HETEROCYCLENE DERIVATIVES AS PEST CONTROL AGENTS

Abstract

The invention relates to novel compounds of the formula (I)

##STR00001##

in which R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, Y, Z, n and m have the definitions given above,
to the use thereof as acaricides and/or insecticides for controlling animal pests, and to methods and intermediates for the preparation thereof.

Claims

1. A compound of formula (I) ##STR00102## in which R.sup.1 represents (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)cyanoalkyl, (C.sub.1-C.sub.6)hydroxyalkyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.2-C.sub.6)haloalkynyl or (C.sub.3-C.sub.8)cycloalkyl, R.sup.2 represents hydrogen, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)cyanoalkyl, (C.sub.1-C.sub.6)hydroxyalkyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkoxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkenyloxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)haloalkenyloxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.2-C.sub.6)cyanoalkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.2-C.sub.6)alkynyloxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)haloalkynyloxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)haloalkynyl, (C.sub.2-C.sub.6)cyanoalkynyl, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)alkyl-(C.sub.3-C.sub.8)cycloalkyl, halo(C.sub.3-C.sub.8)cycloalkyl, cyano(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)alkylthio-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkylthio-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylsulfinyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkylsulfinyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylsulfonyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkylsulfonyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylcarbonyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkylcarbonyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxycarbonyl-(C.sub.1-C.sub.6)alkyl or (C.sub.1-C.sub.6)haloalkoxycarbonyl-(C.sub.1-C.sub.6)alkyl, R.sup.3 represents hydrogen, halogen, cyano, nitro, (C.sub.1-C.sub.6)alkyl, (C.sub.3-C.sub.8)cycloalkyl, cyano(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)haloalkoxy, (C.sub.1-C.sub.6)alkylthio, (C.sub.1-C.sub.6)haloalkylthio, (C.sub.1-C.sub.6)alkylsulfinyl, (C.sub.1-C.sub.6)haloalkylsulfinyl, (C.sub.1-C.sub.6)alkylsulfonyl, (C.sub.1-C.sub.6)haloalkylsulfonyl, SCN, (C.sub.1-C.sub.6)alkylcarbonyl, (C.sub.1-C.sub.6)haloalkylcarbonyl, (C.sub.1-C.sub.6)alkoxycarbonyl, (C.sub.1-C.sub.6)haloalkoxycarbonyl, aminocarbonyl, (C.sub.1-C.sub.6)alkylaminocarbonyl, di(C.sub.1-C.sub.6)alkylaminocarbonyl, (C.sub.1-C.sub.6)haloalkylaminocarbonyl, (C.sub.3-C.sub.8)cycloalkylaminocarbonyl, aminothiocarbonyl, (C.sub.1-C.sub.6)alkylaminothiocarbonyl, di(C.sub.1-C.sub.6)alkylaminothiocarbonyl, (C.sub.1-C.sub.6)haloalkylaminothiocarbonyl, (C.sub.3-C.sub.8)cycloalkylaminothiocarbonyl, amino, (C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylamino, di(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylamino, (C.sub.1-C.sub.6)alkylsulfonylamino, (C.sub.1-C.sub.6)alkylcarbonylamino, (C.sub.1-C.sub.6)haloalkylcarbonylamino, (C.sub.1-C.sub.6)alkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylcarbonylamino, (C.sub.3-C.sub.8)cycloalkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)alkylthiocarbonylamino, (C.sub.1-C.sub.6)haloalkylthiocarbonylamino, (C.sub.1-C.sub.6)alkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylthiocarbonylamino, (C.sub.3-C.sub.8)cycloalkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.2-C.sub.6)cyanoalkenyl, (C.sub.3-C.sub.6)cycloalkyl-(C.sub.2)alkenyl, (C.sub.2-C.sub.6)alkynyl or (C.sub.2-C.sub.6)haloalkynyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.2)alkynyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylaminocarbonylamino, di(C.sub.1-C.sub.6)alkylaminocarbonylamino, (C.sub.3-C.sub.8)cycloalkylaminocarbonylamino, (C.sub.1-C.sub.6)haloalkylaminocarbonylamino, (C.sub.1-C.sub.6)alkylaminocarbonyl-(C.sub.1-C.sub.6)alkylamino, di(C.sub.1-C.sub.6)alkylaminocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylaminocarbonyl-(C.sub.1-C.sub.6)alkylamino or (C.sub.1-C.sub.6)haloalkylaminocarbonyl-(C.sub.1-C.sub.6)alkylamino, or represents a saturated, partially saturated or heteroaromatic ring which is optionally mono- or polysubstituted by identical or different substituents, and in which at least one carbon atom is replaced by a heteroatom, or represents a saturated or partially saturated carbocyclic ring which is mono- or polysubstituted by identical or different substituents, or represents an aromatic ring, where in each case at least one carbonyl group may optionally be present and/or where possible substituents are in each case as follows: cyano, carboxyl, halogen, nitro, acetyl, hydroxy, amino, SCN, SF.sub.5, tri(C.sub.1-C.sub.6)alkylsilyl, (C.sub.3-C.sub.8)cycloalkyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)alkyl-(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)haloalkyl-(C.sub.3-C.sub.8)cycloalkyl, halo(C.sub.3-C.sub.8)cycloalkyl, cyano(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)cyanoalkyl, (C.sub.1-C.sub.6)cyanohaloalkyl, (C.sub.1-C.sub.6)hydroxyalkyl, hydroxycarbonyl-(C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkoxycarbonyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.2-C.sub.6)cyanoalkenyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.2)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.2-C.sub.6)haloalkynyl, (C.sub.2-C.sub.6)cyanoalkynyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)haloalkoxy, (C.sub.1-C.sub.6)cyanoalkoxy, (C.sub.1-C.sub.6)alkoxycarbonyl-(C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkoxyimino, (C.sub.1-C.sub.6)haloalkoxyimino, (C.sub.1-C.sub.6)alkylthio, (C.sub.1-C.sub.6)haloalkylthio, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkylthio, (C.sub.1-C.sub.6)alkylthio-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylsulfinyl, (C.sub.1-C.sub.6)haloalkylsulfinyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkylsulfinyl, (C.sub.1-C.sub.6)alkylsulfinyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylsulfonyl, (C.sub.1-C.sub.6)haloalkylsulfonyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkylsulfonyl, (C.sub.1-C.sub.6)alkylsulfonyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylsulfonyloxy, (C.sub.1-C.sub.6)haloalkylsulfonyloxy, (C.sub.1-C.sub.6)alkylcarbonyl, (C.sub.1-C.sub.6)haloalkylcarbonyl, (C.sub.1-C.sub.6)alkylcarbonyloxy, (C.sub.1-C.sub.6)alkoxycarbonyl, (C.sub.1-C.sub.6)haloalkoxycarbonyl, aminocarbonyl, (C.sub.1-C.sub.6)alkylaminocarbonyl, di(C.sub.1-C.sub.6)alkylaminocarbonyl, (C.sub.1-C.sub.6)haloalkylaminocarbonyl, (C.sub.2-C.sub.6)alkenylaminocarbonyl, di(C.sub.2-C.sub.6)alkenylaminocarbonyl, (C.sub.3-C.sub.8)cycloalkylaminocarbonyl, (C.sub.1-C.sub.6)alkylsulfonylamino, (C.sub.1-C.sub.6)alkylamino, di(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylamino, (C.sub.3-C.sub.8)cycloalkylamino, aminosulfonyl, (C.sub.1-C.sub.6)alkylaminosulfonyl, di(C.sub.1-C.sub.6)alkylaminosulfonyl, (C.sub.1-C.sub.6)alkylsulfoximino, aminothiocarbonyl, (C.sub.1-C.sub.6)alkylaminothiocarbonyl, di(C.sub.1-C.sub.6)alkylaminothiocarbonyl, (C.sub.1-C.sub.6)haloalkylaminothiocarbonyl, (C.sub.3-C.sub.8)cycloalkylaminothiocarbonyl, (C.sub.1-C.sub.6)alkylcarbonylamino, (C.sub.1-C.sub.6)haloalkylcarbonylamino, (C.sub.1-C.sub.6)alkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.6)cycloalkylcarbonylamino, (C.sub.3-C.sub.8)cycloalkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)alkylthiocarbonylamino, (C.sub.1-C.sub.6)haloalkylthiocarbonylamino, (C.sub.1-C.sub.6)alkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylthiocarbonylamino, (C.sub.3-C.sub.8)cycloalkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, hetaryl, oxohetaryl, halohetaryl, halooxohetaryl, cyanohetaryl, cyanooxohetaryl, (C.sub.1-C.sub.6)haloalkylhetaryl or (C.sub.1-C.sub.6)haloalkyloxohetaryl, R.sup.4, R.sup.5, R.sup.6, R.sup.7 independently of one another represent hydrogen, cyano, halogen, (C.sub.1-C.sub.3)alkyl or (C.sub.1-C.sub.3)haloalkyl, Y represents oxygen, ═N—H or ═N—CN, Z represents —NR.sup.8, oxygen or sulfur, where R.sup.8 represents hydrogen, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)cyanoalkyl, (C.sub.1-C.sub.6)hydroxyalkyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkoxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkenyloxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)haloalkenyloxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.2-C.sub.6)cyanoalkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.2-C.sub.6)haloalkynyl or (C.sub.3-C.sub.6)cycloalkyl, m represents 0 or 1, n represents 0 or 1.

2. The compound of the formula (I) as claimed in claim 1, in which R.sup.1 represents (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)cyanoalkyl, (C.sub.1-C.sub.4)alkoxy-(C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.2-C.sub.4)alkenyl, (C.sub.2-C.sub.4)haloalkenyl, (C.sub.2-C.sub.4)alkynyl, (C.sub.2-C.sub.4)haloalkynyl or (C.sub.3-C.sub.6)cycloalkyl, R.sup.2 represents hydrogen, (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)cyanoalkyl, (C.sub.1-C.sub.4)hydroxyalkyl, (C.sub.1-C.sub.4)alkoxy-(C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkoxy-(C.sub.1-C.sub.4)alkyl, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.3-C.sub.6)cycloalkyl-(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)alkyl-(C.sub.3-C.sub.6)cycloalkyl, halo(C.sub.3-C.sub.6)cycloalkyl, cyano(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)alkylthio-(C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkylthio-(C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)alkylsulfinyl-(C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkylsulfinyl-(C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)alkylsulfonyl-(C.sub.1-C.sub.4)alkyl or (C.sub.1-C.sub.4)haloalkylsulfonyl-(C.sub.1-C.sub.4)alkyl, R.sup.3 represents hydrogen, halogen, cyano, nitro, (C.sub.1-C.sub.6)alkyl, (C.sub.3-C.sub.8)cycloalkyl, cyano(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)haloalkoxy, (C.sub.1-C.sub.6)alkylthio, (C.sub.1-C.sub.6)haloalkylthio, (C.sub.1-C.sub.6)alkylsulfinyl, (C.sub.1-C.sub.6)haloalkylsulfinyl, (C.sub.1-C.sub.6)alkylsulfonyl, (C.sub.1-C.sub.6)haloalkylsulfonyl, SCN, (C.sub.1-C.sub.6)alkylcarbonyl, (C.sub.1-C.sub.6)haloalkylcarbonyl, (C.sub.1-C.sub.6)alkoxycarbonyl, (C.sub.1-C.sub.6)haloalkoxycarbonyl, aminocarbonyl, (C.sub.1-C.sub.6)alkylaminocarbonyl, di(C.sub.1-C.sub.6)alkylaminocarbonyl, (C.sub.1-C.sub.6)haloalkylaminocarbonyl, (C.sub.3-C.sub.8)cycloalkylaminocarbonyl, aminothiocarbonyl, (C.sub.1-C.sub.6)alkylaminothiocarbonyl, di(C.sub.1-C.sub.6)alkylaminothiocarbonyl, (C.sub.1-C.sub.6)haloalkylaminothiocarbonyl, (C.sub.3-C.sub.8)cycloalkylaminothiocarbonyl, amino, (C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylamino, di(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylamino, (C.sub.1-C.sub.6)alkylsulfonylamino, (C.sub.1-C.sub.6)alkylcarbonylamino, (C.sub.1-C.sub.6)haloalkylcarbonylamino, (C.sub.1-C.sub.6)alkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylcarbonylamino, (C.sub.3-C.sub.8)cycloalkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)alkylthiocarbonylamino, (C.sub.1-C.sub.6)haloalkylthiocarbonylamino, (C.sub.1-C.sub.6)alkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylthiocarbonylamino, (C.sub.3-C.sub.8)cycloalkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.2-C.sub.6)cyanoalkenyl, (C.sub.3-C.sub.6)cycloalkyl-(C.sub.2)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.2-C.sub.6)haloalkynyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.2)alkynyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylaminocarbonylamino, di(C.sub.1-C.sub.6)alkylaminocarbonylamino, (C.sub.3-C.sub.8)cycloalkylaminocarbonylamino, (C.sub.1-C.sub.6)haloalkylaminocarbonylamino, (C.sub.1-C.sub.6)alkylaminocarbonyl-(C.sub.1-C.sub.6)alkylamino, di(C.sub.1-C.sub.6)alkylaminocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylaminocarbonyl-(C.sub.1-C.sub.6)alkylamino or (C.sub.1-C.sub.6)haloalkylaminocarbonyl-(C.sub.1-C.sub.6)alkylamino, or represents aryl, hetaryl, cyclopentenyl or cyclohexenyl, each of which is optionally mono- or polysubstituted by identical or different substituents, where (in the case of hetaryl) at least one carbonyl group may optionally be present and where possible substituents in each case are as follows: cyano, carboxyl, halogen, nitro, acetyl, hydroxy, amino, SCN, SF.sub.5, tri(C.sub.1-C.sub.6)alkylsilyl, (C.sub.3-C.sub.8)cycloalkyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.6)alkyl-(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)haloalkyl-(C.sub.3-C.sub.8)cycloalkyl, halo(C.sub.3-C.sub.8)cycloalkyl, cyano(C.sub.3-C.sub.8)cycloalkyl, (C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)haloalkyl, (C.sub.1-C.sub.6)cyanoalkyl, (C.sub.1-C.sub.6)cyanohaloalkyl, (C.sub.1-C.sub.6)hydroxyalkyl, hydroxycarbonyl-(C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkoxycarbonyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)haloalkenyl, (C.sub.2-C.sub.6)cyanoalkenyl, (C.sub.3-C.sub.8)cycloalkyl-(C.sub.2)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.2-C.sub.6)haloalkynyl, (C.sub.2-C.sub.6)cyanoalkynyl, (C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)haloalkoxy, (C.sub.1-C.sub.6)cyanoalkoxy, (C.sub.1-C.sub.6)alkoxycarbonyl-(C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkoxy, (C.sub.1-C.sub.6)alkoxyimino, (C.sub.1-C.sub.6)haloalkoxyimino, (C.sub.1-C.sub.6)alkylthio, (C.sub.1-C.sub.6)haloalkylthio, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkylthio, (C.sub.1-C.sub.6)alkylthio-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylsulfinyl, (C.sub.1-C.sub.6)haloalkylsulfinyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkylsulfinyl, (C.sub.1-C.sub.6)alkylsulfinyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylsulfonyl, (C.sub.1-C.sub.6)haloalkylsulfonyl, (C.sub.1-C.sub.6)alkoxy-(C.sub.1-C.sub.6)alkylsulfonyl, (C.sub.1-C.sub.6)alkylsulfonyl-(C.sub.1-C.sub.6)alkyl, (C.sub.1-C.sub.6)alkylsulfonyloxy, (C.sub.1-C.sub.6)haloalkylsulfonyloxy, (C.sub.1-C.sub.6)alkylcarbonyl, (C.sub.1-C.sub.6)haloalkylcarbonyl, (C.sub.1-C.sub.6)alkylcarbonyloxy, (C.sub.1-C.sub.6)alkoxycarbonyl, (C.sub.1-C.sub.6)haloalkoxycarbonyl, aminocarbonyl, (C.sub.1-C.sub.6)alkylaminocarbonyl, di(C.sub.1-C.sub.6)alkylaminocarbonyl, (C.sub.1-C.sub.6)haloalkylaminocarbonyl, (C.sub.2-C.sub.6)alkenylaminocarbonyl, di(C.sub.2-C.sub.6)alkenylaminocarbonyl, (C.sub.3-C.sub.8)cycloalkylaminocarbonyl, (C.sub.1-C.sub.6)alkylsulfonylamino, (C.sub.1-C.sub.6)alkylamino, di(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylamino, (C.sub.3-C.sub.8)cycloalkylamino, aminosulfonyl, (C.sub.1-C.sub.6)alkylaminosulfonyl, di(C.sub.1-C.sub.6)alkylaminosulfonyl, (C.sub.1-C.sub.6)alkylsulfoximino, aminothiocarbonyl, (C.sub.1-C.sub.6)alkylaminothiocarbonyl, di(C.sub.1-C.sub.6)alkylaminothiocarbonyl, (C.sub.1-C.sub.6)haloalkylaminothiocarbonyl, (C.sub.3-C.sub.8)cycloalkylaminothiocarbonyl, (C.sub.1-C.sub.6)alkylcarbonylamino, (C.sub.1-C.sub.6)haloalkylcarbonylamino, (C.sub.1-C.sub.6)alkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.6)cycloalkylcarbonylamino, (C.sub.3-C.sub.8)cycloalkylcarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)alkylthiocarbonylamino, (C.sub.1-C.sub.6)haloalkylthiocarbonylamino, (C.sub.1-C.sub.6)alkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.1-C.sub.6)haloalkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, (C.sub.3-C.sub.8)cycloalkylthiocarbonylamino, (C.sub.3-C.sub.8)cycloalkylthiocarbonyl-(C.sub.1-C.sub.6)alkylamino, hetaryl, oxohetaryl, halohetaryl, halooxohetaryl, cyanohetaryl, cyanooxohetaryl, (C.sub.1-C.sub.6)haloalkylhetaryl or (C.sub.1-C.sub.6)haloalkyloxohetaryl, R.sup.4, R.sup.5, R.sup.6, R.sup.7 independently of one another represent hydrogen, cyano, halogen, (C.sub.1-C.sub.3)alkyl or (C.sub.1-C.sub.3)haloalkyl, Y represents oxygen, ═N—H or ═N—CN, Z represents —NR.sup.8, oxygen or sulfur, where R.sup.8 represents hydrogen, (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)cyanoalkyl, (C.sub.1-C.sub.4)hydroxyalkyl, (C.sub.1-C.sub.4)alkoxy-(C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkoxy-(C.sub.1-C.sub.4)alkyl, (C.sub.2-C.sub.4)alkenyl, (C.sub.2-C.sub.4)alkenyloxy-(C.sub.1-C.sub.4)alkyl, (C.sub.2-C.sub.4)haloalkenyloxy-(C.sub.1-C.sub.4)alkyl, (C.sub.2-C.sub.4)haloalkenyl, (C.sub.2-C.sub.4)cyanoalkenyl, (C.sub.2-C.sub.4)alkynyl, (C.sub.2-C.sub.4)haloalkynyl or (C.sub.3-C.sub.6)cycloalkyl, m represents 0 or 1, n represents 0 or 1.

3. The compound of the formula (I) as claimed in claim 1, in which R.sup.1 represents (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.2-C.sub.4)alkenyl, (C.sub.2-C.sub.4)haloalkenyl or (C.sub.3-C.sub.6)cycloalkyl, R.sup.2 represents hydrogen, (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.3-C.sub.6)cycloalkyl or halo(C.sub.3-C.sub.6)cycloalkyl, R.sup.3 represents hydrogen, halogen, cyano, (C.sub.1-C.sub.4)alkyl, (C.sub.3-C.sub.6)cycloalkyl, cyano(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)haloalkoxy, aminocarbonyl, (C.sub.1-C.sub.4)alkylaminocarbonyl, di(C.sub.1-C.sub.4)alkylaminocarbonyl, (C.sub.1-C.sub.4)haloalkylaminocarbonyl, (C.sub.3-C.sub.6)cycloalkylaminocarbonyl, amino, (C.sub.1-C.sub.4)alkylamino, (C.sub.1-C.sub.4)haloalkylamino, di(C.sub.1-C.sub.4)alkylamino, (C.sub.3-C.sub.6)cycloalkylamino, (C.sub.1-C.sub.4)alkylsulfonylamino, (C.sub.1-C.sub.4)alkylcarbonylamino, (C.sub.1-C.sub.4)haloalkylcarbonylamino, (C.sub.1-C.sub.4)alkylcarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.1-C.sub.4)haloalkylcarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.3-C.sub.6)cycloalkylcarbonylamino, (C.sub.3-C.sub.6)cycloalkylcarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.2-C.sub.4)alkenyl, (C.sub.2-C.sub.4)haloalkenyl, (C.sub.2-C.sub.4)cyanoalkenyl or (C.sub.3-C.sub.6)cycloalkyl-(C.sub.2)alkenyl, or represents phenyl, pyridyl, pyrimidyl, pyridazinyl, thiophenyl, furanyl, pyrazolyl, thiazolyl, oxazolyl or imidazolyl, each of which is optionally mono- or polysubstituted by identical or different substituents, where (in the case of hetaryl) at least one carbonyl group may optionally be present and where possible substituents in each case are as follows: cyano, halogen, nitro, acetyl, hydroxy, amino, SF.sub.5, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)alkyl-(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)haloalkyl-(C.sub.3-C.sub.6)cycloalkyl, halo(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)alkyl, cyano(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)cyanoalkyl, (C.sub.1-C.sub.4)cyanohaloalkyl, (C.sub.1-C.sub.4)hydroxyalkyl, (C.sub.1-C.sub.4)alkoxy-(C.sub.1-C.sub.2)alkyl, (C.sub.2-C.sub.4)alkenyl, (C.sub.2-C.sub.4)haloalkenyl, (C.sub.2-C.sub.4)cyanoalkenyl, (C.sub.3-C.sub.6)cycloalkyl-(C.sub.2)alkenyl, (C.sub.2-C.sub.4)alkynyl, (C.sub.2-C.sub.4)haloalkynyl, (C.sub.2-C.sub.4)cyanoalkynyl, (C.sub.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)haloalkoxy, (C.sub.1-C.sub.4)cyanoalkoxy, (C.sub.1-C.sub.4)alkoxy-(C.sub.1-C.sub.2)alkoxy, (C.sub.1-C.sub.4)alkoxyimino, (C.sub.1-C.sub.4)haloalkoxyimino, (C.sub.1-C.sub.4)alkylthio, (C.sub.1-C.sub.4)haloalkylthio, (C.sub.1-C.sub.4)alkylthio-(C.sub.1-C.sub.2)alkyl, (C.sub.1-C.sub.4)alkylsulfinyl, (C.sub.1-C.sub.4)haloalkylsulfinyl, (C.sub.1-C.sub.4)alkylsulfonyl, (C.sub.1-C.sub.4)haloalkylsulfonyl, (C.sub.1-C.sub.4)alkylsulfonyloxy, (C.sub.1-C.sub.4)haloalkylsulfonyloxy, (C.sub.1-C.sub.4)alkylcarbonyl, (C.sub.1-C.sub.4)haloalkylcarbonyl, aminocarbonyl, (C.sub.1-C.sub.4)alkylaminocarbonyl, (C.sub.1-C.sub.4)haloalkylaminocarbonyl, di(C.sub.1-C.sub.4)alkylaminocarbonyl, (C.sub.3-C.sub.6)cycloalkylaminocarbonyl, aminothiocarbonyl, (C.sub.1-C.sub.4)alkylaminothiocarbonyl, di(C.sub.1-C.sub.4)alkylaminothiocarbonyl, (C.sub.1-C.sub.4)haloalkylaminothiocarbonyl, (C.sub.3-C.sub.6)cycloalkylaminothiocarbonyl, (C.sub.1-C.sub.4)alkylsulfonylamino, (C.sub.1-C.sub.4)alkylamino, di(C.sub.1-C.sub.4)alkylamino, (C.sub.1-C.sub.4)haloalkylamino, (C.sub.3-C.sub.6)cycloalkylamino, aminosulfonyl, (C.sub.1-C.sub.4)alkylaminosulfonyl, di(C.sub.1-C.sub.4)alkylaminosulfonyl, (C.sub.1-C.sub.4)alkylcarbonylamino, (C.sub.1-C.sub.4)haloalkylcarbonylamino, (C.sub.1-C.sub.4)alkylcarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.1-C.sub.2)haloalkylcarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.3-C.sub.6)cycloalkylcarbonylamino, (C.sub.3-C.sub.6)cycloalkylcarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.1-C.sub.4)alkylthiocarbonylamino, (C.sub.1-C.sub.4)haloalkylthiocarbonylamino, (C.sub.1-C.sub.4)alkylthiocarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.1-C.sub.4)haloalkylthiocarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.3-C.sub.6)cycloalkylthiocarbonylamino, (C.sub.3-C.sub.6)cycloalkylthiocarbonyl-(C.sub.1-C.sub.2)alkylamino or pyridyl which is optionally substituted by halogen, R.sup.4, R.sup.5, R.sup.6, R.sup.7 are identical and represent either hydrogen or fluorine, Y represents oxygen or ═N—H, Z represents —NR.sup.8 or oxygen, where R.sup.8 represents hydrogen or (C.sub.1-C.sub.4)alkyl, m represents 0 or 1, n represents 0 or 1.

4. The compound of the formula (I) as claimed in claim 1, in which R.sup.1 represents methyl, ethyl, n-propyl, isopropyl, cyclopropyl, fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl or pentafluoroethyl, R.sup.2 represents hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, tert-butyl, cyclobutyl, fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl or pentafluoroethyl, R.sup.3 represents hydrogen, halogen, (C.sub.1-C.sub.4)alkyl, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.2-C.sub.4)alkenyl, (C.sub.2-C.sub.4)haloalkenyl, (C.sub.2-C.sub.4)cyanoalkenyl or (C.sub.3-C.sub.6)cycloalkyl-(C.sub.2)alkenyl, or represents phenyl, pyridyl, pyrimidyl, pyridazinyl, thiophenyl, thiazolyl, oxazolyl or imidazolyl, each of which is optionally mono- or polysubstituted by identical or different substituents and bridged via a carbon atom to the rest of the molecule, where possible substituents in each case are as follows: cyano, fluorine, chlorine, bromine, nitro, acetyl, hydroxy, amino, SF.sub.5, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)alkyl-(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)haloalkyl-(C.sub.3-C.sub.6)cycloalkyl, halo(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)alkyl, cyano(C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)cyanoalkyl, (C.sub.1-C.sub.4)hydroxyalkyl, (C.sub.1-C.sub.4)alkoxy-(C.sub.1-C.sub.2)alkyl, (C.sub.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)haloalkoxy, (C.sub.1-C.sub.4)alkoxy-(C.sub.1-C.sub.2)alkoxy, (C.sub.1-C.sub.4)alkoxyimino, (C.sub.1-C.sub.4)alkylthio, (C.sub.1-C.sub.4)haloalkylthio, (C.sub.1-C.sub.4)alkylsulfinyl, (C.sub.1-C.sub.4)haloalkylsulfinyl, (C.sub.1-C.sub.4)alkylsulfonyl, (C.sub.1-C.sub.4)haloalkylsulfonyl, (C.sub.1-C.sub.4)alkylcarbonyl, aminocarbonyl, (C.sub.1-C.sub.4)alkylaminocarbonyl, di(C.sub.1-C.sub.4)alkylaminocarbonyl, (C.sub.1-C.sub.4)haloalkylaminocarbonyl, (C.sub.3-C.sub.6)cycloalkylaminocarbonyl, (C.sub.1-C.sub.4)alkylsulfonylamino, (C.sub.1-C.sub.4)alkylamino, di(C.sub.1-C.sub.4)alkylamino, (C.sub.1-C.sub.4)haloalkylamino, (C.sub.3-C.sub.6)cycloalkylamino, (C.sub.1-C.sub.4)alkylcarbonylamino, (C.sub.1-C.sub.4)haloalkylcarbonylamino, (C.sub.1-C.sub.4)alkylcarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.1-C.sub.4)haloalkylcarbonyl-(C.sub.1-C.sub.2)alkylamino, (C.sub.3-C.sub.6)cycloalkylcarbonylamino, (C.sub.3-C.sub.6)cycloalkylcarbonyl-(C.sub.1-C.sub.2)alkylamino or pyridyl which is optionally monosubstituted by chlorine or bromine, or represents pyrazolyl, triazolyl or imidazolyl, each of which is optionally mono- or polysubstituted by identical or different substituents and bridged via a nitrogen atom to the rest of the molecule, where possible substituents in each case are as follows: cyano, fluorine, chlorine, bromine, nitro, hydroxy, amino, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.1-C.sub.4)alkyl, (C.sub.1-C.sub.4)haloalkyl, (C.sub.1-C.sub.4)alkoxy, (C.sub.1-C.sub.4)haloalkoxy or aminocarbonyl, R.sup.4, R.sup.5, R.sup.6, R.sup.7 are identical and represent either hydrogen or fluorine, Y represents oxygen or ═N—H, Z represents —NR.sup.8 or oxygen, where R.sup.8 represents hydrogen or methyl, m represents 0 or 1, n represents 0 or 1.

5. The compound of the formula (I) as claimed in claim 1, in which R.sup.1 represents ethyl, R.sup.2 represents methyl, R.sup.3 represents hydrogen, bromine, cyclopropyl, trifluoromethyl, tetrafluoroethyl, pentafluoroethyl or represents phenyl, pyridyl, pyrimidyl, pyridazinyl, thiophenyl, thiazolyl, oxazolyl or imidazolyl, each of which is optionally mono- or polysubstituted by identical or different substituents and bridged via a carbon atom to the rest of the molecule, where possible substituents in each case are as follows: cyano, fluorine, chlorine, bromine, methyl, trifluoromethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, SF.sub.5, 2-cyano-2-propyl, cyclopropyl, 1-cyano-1-cyclopropyl, 1-fluoro-1-cyclopropyl, 1-trifluoromethyl-1-cyclopropyl or pyridyl which is optionally monosubstituted by chlorine or bromine, or represents triazolyl which is optionally monosubstituted and bridged via a nitrogen atom to the rest of the molecule, where possible substituents in each case are as follows: cyano, fluorine, chlorine, bromine, trifluoromethyl or cyclopropyl, R.sup.4, R.sup.5, R.sup.6, R.sup.7 represent fluorine, Y represents oxygen or ═N—H, Z represents —NR.sup.8, where R.sup.8 represents hydrogen or methyl, m represents 0 or 1, n represents 0 or 1.

6. The compound of the formula (I) as claimed in claim 1, in which R.sup.1 represents ethyl, R.sup.2 represents methyl, R.sup.3 represents bromine, cyclopropyl, or phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, trifluoromethyl, 1-cyano-1-cyclopropyl, 1-trifluoromethyl-1-cyclopropyl or 1-fluoro-1-cyclopropyl, or represents pyridyl which is optionally monosubstituted and bridged via a carbon atom to the rest of the molecule, where possible substituents in each case are as follows: cyano, chlorine, bromine, cyclopropyl or 1-cyano-1-cyclopropyl, or represents thiophenyl or thiazolyl, each of which is optionally monosubstituted and bridged via a carbon atom to the rest of the molecule, where possible substituents in each case are as follows: chlorine or 1-cyano-1-cyclopropyl, or represents triazolyl which is optionally monosubstituted and bridged via a nitrogen atom to the rest of the molecule, where possible substituents in each case are as follows: cyclopropyl, R.sup.4, R.sup.5, R.sup.6, R.sup.7 represent fluorine, Y represents oxygen, Z represents —NR.sup.8, where R.sup.8 represents hydrogen or methyl, m and n represent 0 or m and n represent 1.

7. The compound of the formula (I) as claimed in claim 1, in which R.sup.1 represents ethyl, R.sup.2 represents methyl, R.sup.3 represents hydrogen, bromine, cyclopropyl, or phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, trifluoromethyl, 1-cyano-1-cyclopropyl, 1-trifluoromethyl-1-cyclopropyl or 1-fluoro-1-cyclopropyl, or phenyl which is optionally disubstituted by identical or different substituents from the group of fluorine, chlorine, bromine, cyano, or represents pyridyl which is optionally monosubstituted and bridged via a carbon atom to the rest of the molecule, where possible substituents in each case are as follows: cyano, chlorine, bromine, cyclopropyl, 1-cyano-1-cyclopropyl or pyridyl which is monosubstituted by chlorine or bromine (where pyridyl is bridged via a carbon atom to the rest of the molecule), or represents thiophenyl or thiazolyl, each of which is optionally monosubstituted and bridged via a carbon atom to the rest of the molecule, where possible substituents in each case are as follows: chlorine, or represents triazolyl which is optionally monosubstituted and bridged via a nitrogen atom to the rest of the molecule, where possible substituents in each case are as follows: cyclopropyl, R.sup.4, R.sup.5, R.sup.6, R.sup.7 represent fluorine, Y represents oxygen or ═N—H, Z represents —NR.sup.8, where R.sup.8 represents hydrogen or methyl, m and n represent 0 or m and n represent 1.

8. The compound of the formula (I) as claimed in claim 1, in which the compounds have the structures below: I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-29, I-30, I-31, I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-39, I-40, I-41, I-42, I-43, I-44.

9. An agrochemical formulation comprising a compound of formula (I) as claimed in claim 1, and one or more extenders and/or surfactants.

10. The agrochemical formulation as claimed in claim 9, additionally comprising a further active agrochemical ingredient.

11. A method for controlling one or more animal pests, comprising allowing a compound of formula (I) as claimed in claim 1 or an agrochemical formulation thereof to act on the animal pests and/their a habitat thereof.

12. A product comprising a compound of formula (I) as claimed in claim 1 or an agrochemical formulation thereof as for controlling one or more animal pests.

Description

PREPARATION EXAMPLES

Intermediates

Intermediate 1A

Ethyl 2-bromo-1-methyl-1H-imidazole-4-carboxylate

[0598] ##STR00009##

[0599] 30.0 g (195 mmol) of ethyl 1-methyl-1H-imidazole-4-carboxylate were dissolved in 1.0 l of tetrahydrofuran and cooled to 0° C. To this solution 34.5 g (195 mmol) of N-bromosuccinimide were added in portions, and the reaction mixture was stirred at room temperature overnight. The reaction was terminated by the addition of saturated sodium thiosulfate solution (Na.sub.2S.sub.2O.sub.3), and 800 ml of ethyl acetate were added. The phases were separated and extraction was performed three times with 800 ml of ethyl acetate each time. The organic phases were combined, dried over sodium sulfate and filtered. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography purification using a petroleum ether/ethyl acetate gradient (3:1) as mobile phase.

[0600] .sup.1H-NMR (300 MHz, d.sub.6-DMSO) δ ppm: 1.26 (t, 3H), 3.64 (s, 3H), 4.22 (q, 2H), 8.07 (s, 1H).

Intermediate 2A

2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazole-4-carboxylic acid

[0601] ##STR00010##

[0602] 31.0 g (134 mmol) of ethyl 2-bromo-1-methyl-1H-imidazole-4-carboxylate and 24.4 g (200 mmol) of diethyl disulfide were dissolved in 620 ml of tetrahydrofuran and cooled to Q 78° C. To this solution were added dropwise 100 ml (2M in THF, 200 mmol) of lithium diisopropylamide (LDA) and the reaction mixture was stirred at Q 78° C. for 30 minutes. The reaction was terminated by adding saturated ammonium chloride solution. The phases were separated and the aqueous phase was extracted three times with 300 ml of ethyl acetate each time. The organic phases were combined, dried over magnesium sulfate and filtered. The solvent was distilled off under reduced pressure and the residue was purified by column chromatography purification using a petroleum ether/ethyl acetate gradient as mobile phase. This gave 28.5 g (97.3 mmol) of ethyl 2-bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazole-4-carboxylate. This was dissolved in 300 ml of methanol and the solution was cooled to 0° C. 300 ml of sodium hydroxide (2N in water, 600 mmol) were then added and the mixture was stirred at room temperature for 1 h. The mixture was concentrated on a rotary evaporator and neutralized by adding 1N HCl. The mixture was then extracted with ethyl acetate. The solvent was distilled off under reduced pressure and the target compound was obtained.

[0603] .sup.1H-NMR (300 MHz, d.sub.6-DMSO) δ ppm: 1.09 (t, 3H), 2.86 (q, 2H), 3.64 (s, 3H), 12.60 (s, 1H).

Intermediate 3A

N-(7-Amino-2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)-2-bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazole-4-carboxamide

[0604] ##STR00011##

[0605] To an initial charge of 2-bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazole-4-carboxylic acid (557 mg, 2.10 mmol) in DMF (40.0 ml) was added, at room temperature, HATU (957 mg, 2.52 mmol), and the mixture was stirred for 30 min. The mixture was then cooled to −10° C. and a solution of 2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxine-6,7-diamine (500 mg, 2.10 mmol) in DMF (10.0 ml) was slowly added dropwise thereto. After the addition had ended, the mixture was stirred at −10° C. for 1 h. The mixture was then poured into water and extracted with dichloromethane. The combined organic phases were washed twice with 1.0 M hydrochloric acid and once with saturated aqueous sodium chloride solution and dried over sodium sulfate. Concentration of the solution to dryness afforded the title compound (1.34 g, 73% purity, 96% of theory). The title compound obtained was reacted further without further purification.

[0606] ESI Mass [m/z]: 484.9/486.9 [M+H].sup.+

Intermediate 4A

4,4,5,5-Tetramethyl-2-{4-[1-(trifluoromethyl)cyclopropyl]phenyl}-1,3,2-dioxaborolane

[0607] ##STR00012##

[0608] A mixture of 1-bromo-4-[1-(trifluoromethyl)cyclopropyl]benzene (250 mg, 943 μmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (287 mg, 1132 μmol), Pd(dppf)Cl.sub.2*CH.sub.2Cl.sub.2, (34.65 mg, 47 μmol) and potassium acetate (278 mg, 2.83 mmol) in acetonitrile (4.0 ml) were heated in a microwave reactor to 150° C. for 15 min. After cooling to RT, the reaction mixture was concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (281 mg, 81% purity, 77% of theory).

[0609] ESI Mass [m/z]: 313.1 [M+H].sup.+

[0610] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.68 (d, 2H), 7.47 (d, 2H), 1.37-1.32 (m, 2H), 1.29 (s, 12H), 1.15-1.09 (m, 2H).

Intermediate 5A

tert-Butyl 2-cyclopropyl-1-methyl-1H-imidazole-4-carboxylate

[0611] ##STR00013##

[0612] To a solution of tert-butyl 2-bromo-1-methyl-1H-imidazole-4-carboxylate (10.0 g, 38.3 mmol) in THF (300 ml) was added a solution of potassium phosphate (16.0 g, 116 mmol) in water (60 ml). The mixture was stirred under an inert atmosphere for 10 min before adding X-Phos Pd G2 (CAS: 1310584-14-5, 2.00 g, 2.54 mmol). The mixture was heated to boiling and then a solution of cyclopropylboronic acid (10.0 g, 116 mmol) in THF (100 ml) was added dropwise over a period of 8 h. After the addition had ended, the mixture was refluxed further overnight, before more potassium phosphate (16.0 g, 116 mmol) followed by a solution of cyclopropylboronic acid (10.0 g, 116 mmol) in THF (100 ml) were added. After the addition had ended, the reaction mixture was refluxed for a further 16 h. After cooling to RT, the mixture was diluted with water (1000 ml) and extracted with ethyl acetate (2×500 ml). The combined organic phases were washed with saturated aqueous sodium chloride solution, dried over sodium sulfate, filtered through a thin layer of silica gel and concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (4.0 g, 49% of theory).

Intermediate 6A

tert-Butyl 5-bromo-2-cyclopropyl-1-methyl-1H-imidazole-4-carboxylate

[0613] ##STR00014##

[0614] To a solution of tert-butyl 2-cyclopropyl-1-methyl-1H-imidazole-4-carboxylate (6.00 g, 27.0 mmol) in dichloromethane (100 ml) was added a solution of sodium hydrogencarbonate (2.88 g, 34.3 mmol) in water (12 ml). A solution of bromine (1.73 ml, 33.8 mmol) in dichloromethane (20.0 ml) was added dropwise while cooling with an ice bath. After the addition had ended, the reaction mixture was stirred at RT overnight. Then, the solution was diluted with dichloromethane (200 ml) and washed in succession with saturated aqueous sodium hydrogencarbonate solution (150 ml), saturated aqueous sodium thiosulfate solution (150 ml) and saturated aqueous sodium chloride solution (150 ml). The organic phase was dried over sodium sulfate and concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (7.00 g, 23.2 mmol, 86% of theory).

Intermediate 7A

tert-Butyl 2-cyclopropyl-5-(ethylsulfanyl)-1-methyl-1H-imidazole-4-carboxylate

[0615] ##STR00015##

[0616] n-Butyllithium (2.5 M solution in hexane fraction, 23.0 ml, 57.5 mmol) was added dropwise at −80° C. to a solution of tert-butyl 5-bromo-2-cyclopropyl-1-methyl-1H-imidazole-4-carboxylate (13.0 g, 43.0 mmol) in THF (200 ml). After the addition had ended, the mixture was stirred at −80° C. for a further 1 h, before adding diethyl disulfide (30.0 g, 250 mmol) dropwise. After the addition had ended, the mixture was stirred at 50° C. overnight. After cooling to RT, saturated aqueous ammonium chloride solution (200 ml) was added to the reaction mixture and the mixture was extracted with ethyl acetate (3×300 ml). The combined organic phases were washed with water, dried over sodium sulfate and concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (7.20 g, 25.5 mmol, 78% of theory).

Intermediate 8A

tert-Butyl 2-cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazole-4-carboxylate

[0617] ##STR00016##

[0618] meta-Chloroperbenzoic acid (13.5 g, 78.0 mmol) was added at 0° C. to a solution of tert-butyl 2-cyclopropyl-5-(ethylsulfanyl)-1-methyl-1H-imidazole-4-carboxylate (7.20 g, 25.5 mmol) in dichloromethane (100 ml) and the mixture was then stirred at RT for 24 h. The reaction mixture was then cooled to 0° C., saturated aqueous sodium hydrogencarbonate solution (150 ml) and saturated aqueous sodium thiosulfate solution (150 ml) were added thereto, and this mixture was filtered. The phases were separated and the organic phase was dried over sodium sulfate and concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (7.80 g, 24.8 mmol, 90% of theory).

Intermediate 9A

2-Cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazole-4-carboxylic acid

[0619] ##STR00017##

[0620] Trifluoroacetic acid (10 ml) was added at 0° C. to a solution of tert-butyl 2-cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazole-4-carboxylate (7.80 g, 24.8 mmol) in dichloromethane (100 ml). After the addition had ended, the mixture was stirred at RT for 4 days. The mixture was then concentrated and the residue was stirred in a mixture of MTBE and hexane (1:1). The solids were filtered off. Recrystallization of the thus-obtained crude product from diethyl ether afforded the title compound (6.00 g, 23.2 mmol, 93% of theory).

Intermediate 10A

N-(7-Amino-2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)-2-cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazole-4-carboxamide

[0621] ##STR00018##

[0622] To an initial charge of 2-cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazole-4-carboxylic acid (163 mg, 0.63 mmol) in DMF were added HATU (287.1 mg, 0.76 mmol) and DIPEA (274 μmol, 1.58 mmol). The mixture was stirred at RT for 30 min and then cooled to −10° C. At this temperature, a solution of 2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxine-6,7-diamine (150 mg, 0.63 mmol) in DMF was slowly added dropwise. After the addition had ended, the mixture was stirred at −10° C. for a further 1 h. Then more HATU (287.1 mg, 0.76 mmol) and DIPEA (274 μmol, 1.58 mmol) were added and the mixture was stirred at RT for 1 h. Water was added and the reaction mixture was extracted with dichloromethane. The combined organic phases were washed twice with 1.0 M hydrochloric acid and once with saturated aqueous sodium chloride solution, dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (163 mg, 54% of theory).

[0623] ESI Mass [m/z]: 479.4 [M+H].sup.+

[0624] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=9.65 (s, 1H), 7.38 (s, 1H), 6.71 (s, 1H), 5.26 (s, 2H), 3.91 (s, 3H), 3.61 (q, 2H), 2.21-2.10 (m, 1H), 1.21 (t, 3H), 1.08-0.99 (m, 4H).

Intermediate 11A

2-[4-(1-Fluorocyclopropyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0625] ##STR00019##

[0626] A mixture of 1-bromo-4-(1-fluorocyclopropyl)benzene (200 mg, 930 μmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (283 mg, 1116 μmol), Pd(dppf)Cl.sub.2*CH.sub.2Cl.sub.2, (34.0 mg, 46 μmol) and potassium acetate (274 mg, 2.79 mmol) in acetonitrile (8.0 ml) were heated in a microwave reactor to 150° C. for 15 min. After cooling to RT, the reaction mixture was concentrated. Repeated column chromatography purification of the residue first on silica gel and then by means of preparative HPLC afforded the title compound (79.4 mg, 93% purity, 30% of theory).

[0627] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.68 (d, 2H), 7.26 (d, 2H), 1.57-1.42 (m, 2H), 1.29 (s, 12H), 1.25-1.13 (m, 2H).

Intermediate 12A

4,4,5,5-Tetramethyl-2-{3-[1-(trifluoromethyl)cyclopropyl]phenyl}-1,3,2-dioxaborolane

[0628] ##STR00020##

[0629] A mixture of 1-bromo-3-[1-(trifluoromethyl)cyclopropyl]benzene (200 mg, 755 μmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (229 mg, 905 μmol), Pd(dppf)Cl.sub.2, (25.1 mg, 34 μmol) and potassium acetate (222 mg, 2.26 mmol) in acetonitrile (8.0 ml) were heated in a microwave reactor to 150° C. for 15 min. After cooling to RT, the reaction mixture was filtered through Celite, washed with acetonitrile and the filtrate was concentrated. Repeated column chromatography purification of the residue first on silica gel and then by means of preparative HPLC afforded the title compound (152 mg, 77% purity, 50% of theory).

[0630] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.74 (s, 1H), 7.68-7.64 (m, 1H), 7.61-7.57 (m, 1H), 7.45-7.39 (m, 1H), 1.36-1.32 (m, 2H), 1.30 (s, 12H), 1.15-1.09 (m, 2H).

Intermediate 13A

2-[3-(1-Fluorocyclopropyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

[0631] ##STR00021##

[0632] A mixture of 1-bromo-3-(1-fluorocyclopropyl)benzene (200 mg, 930 μmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane (283 mg, 1116 μmol), Pd(dppf)Cl.sub.2, (31.0 mg, 42 μmol) and potassium acetate (274 mg, 2.79 mmol) in acetonitrile (8.0 ml) were heated in a microwave reactor to 150° C. for 15 min. After cooling to RT, the reaction mixture was filtered through Celite, washed with acetonitrile and the filtrate was concentrated. Repeated column chromatography purification of the residue first on silica gel and then by means of preparative HPLC afforded the title compound (50.4 mg, 72% purity, 15% of theory).

[0633] ESI Mass [m/z]: 263.2 [M+H].sup.+

[0634] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.64-7.57 (m, 2H), 7.44-7.35 (m, 2H), 1.53-1.38 (m, 2H), 1.34-1.27 (m, 12H), 1.18-1.11 (m, 2H).

Intermediate 14A

6,6,7,7-Tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0635] ##STR00022##

[0636] A mixture of 2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxine-6,7-diamine (1.00 g, 4.19 mmol) and formic acid (5.0 ml) was heated in a microwave reactor to 150° C. for 30 min. After cooling to RT, the reaction mixture was concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (588 mg, 56% of theory).

[0637] ESI Mass [m/z]: 249.1 [M+H].sup.+

[0638] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=12.77 (br s, 1H), 8.36 (s, 1H), 7.70 (br s, 2H).

Intermediate 15A

6,6,7,7-Tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0639] ##STR00023##

[0640] 6,6,7,7-Tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (644 mg, 2.59 mmol) was split between four reaction vessels (161 mg, 0.65 mmol each). Iodomethane (101 μl, 1.62 mmol), potassium carbonate (314 mg, 2.27 mmol) and acetone (1.5 ml) were added to each of the vessels. The vessels were sealed and heated to 60° C. for 3 h. After cooling to RT, the four reaction mixtures were combined and partitioned between 1.0 M hydrochloric acid and dichloromethane. The aqueous phase was neutralized with 1.0 M aqueous sodium hydroxide solution and extracted exhaustively with ethyl acetate. All organic phases were combined, washed with saturated aqueous sodium chloride solution, dried over sodium sulfate and concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (345 mg, 51% of theory).

[0641] ESI Mass [m/z]: 263.3 [M+H].sup.+

[0642] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.34 (s, 1H), 7.81 (s, 1H), 7.77 (s, 1H), 3.84 (s, 3H).

WORKING EXAMPLES

Example I-1

2-[2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0643] ##STR00024##

[0644] A mixture of N-(7-amino-2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)-2-bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazole-4-carboxamide (1.02 g, 73% purity, 1.53 mmol) and toluene-4-sulfonic acid monohydrate (878 mg, 4.59 mmol) in toluene (40 ml) was heated to boiling for 2 h. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the organic phase was washed with water until a neutral reaction was achieved, and dried and concentrated. The residue was purified by means of preparative HPLC. This afforded two fractions of the title compound. Fraction 1: 207 mg (98% purity, 28% of theory); fraction 2: 144 mg (88% purity, 18% of theory).

[0645] ESI Mass [m/z]: 467.0/469.0 [M+H].sup.+

[0646] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.70-7.48 (m, 2H), 3.72 (s, 3H), 3.03 (q, 2H), 1.11 (t, 3H).

Example I-2

2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0647] ##STR00025##

[0648] Formic acid (0.325 ml, 8.61 mmol) and hydrogen peroxide (35% aqueous solution, 1.04 ml, 12.0 mmol) were added in succession at RT to a solution of 2-[2-bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (805 mg, 1.72 mmol) in dichloromethane (5.0 ml). The reaction mixture was stirred at RT overnight. Water and saturated aqueous sodium bisulfite solution were then added to the mixture while cooling with ice, and the mixture was stirred at RT for a further night. The mixture was diluted with water (50 ml) and dichloromethane (100 ml). The phases were separated, and the organic phase was washed first with water and then with saturated aqueous sodium hydrogencarbonate solution, dried over sodium sulfate and concentrated. Acetonitrile (4.0 ml) was added to the residue and the mixture was stirred at RT. Filtering off the solids and drying them afforded a first amount of the target compound (485 mg, 92% purity, 41% of theory). The mother liquor was concentrated and the residue was purified by column chromatography on silica gel, resulting in the isolation of further title compound (114 mg, 93% purity, 12% of theory).

[0649] ESI Mass [m/z]: 498.9/500.9 [M+H].sup.+

[0650] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=13.37 (s, 1H), 7.81 (br s, 1H), 7.53 (br s, 1H), 4.03 (q, 2H), 3.91 (s, 3H), 1.28 (t, 3H).

Example I-3

2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0651] ##STR00026##

[0652] To an initial charge of 2-[2-bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (495 mg, 0.99 mmol) in acetone were added potassium carbonate (480 mg, 3.47 mmol) and iodomethane (154 μl, 2.47 mmol). The mixture was heated to boiling for 2 h. After cooling to RT, the reaction mixture was concentrated to dryness. The residue was taken up in dichloromethane and washed with 1.0 M hydrochloric acid. The organic phase was washed with saturated aqueous sodium chloride solution and dried over sodium sulfate. Concentration of the obtained solution to dryness afforded the title compound (469 mg, 90% purity, 83% of theory).

[0653] ESI Mass [m/z]: 513.0/515.0 [M+H].sup.+

[0654] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.83 (s, 1H), 3.91 (s, 3H), 3.77 (s, 3H), 3.73 (q, 2H), 1.26 (t, 3H).

Example I-4

2-[2-(4-Chlorophenyl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0655] ##STR00027##

[0656] A mixture of dioxane (2.6 ml) and 1.0 M aqueous sodium carbonate solution (3.1 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (100 mg, 195 μmol), (4-chlorophenyl)boronic acid (30.5 mg, 195 μmol) and tetrakis(triphenylphosphine)palladium(0) (11.2 mg, 10 μmol) were then added and the mixture was heated at 92° C. overnight. After cooling to RT, the reaction mixture was concentrated to dryness and the residue was taken up in water and dichloromethane. The phases were separated, and the organic phase was washed twice with water and then dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (49.3 mg, 88% purity, 52% of theory).

[0657] ESI Mass [m/z]: 545.0 [M+H].sup.+

[0658] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.87-7.79 (m, 3H), 7.67 (d, 2H), 3.95 (s, 3H), 3.84-3.76 (m, 5H), 1.31 (t, 3H).

Example I-5

2-[5-(Ethylsulfonyl)-2-(4-fluorophenyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0659] ##STR00028##

[0660] A mixture of dioxane (1.0 ml) and 1.0 M aqueous sodium carbonate solution (1.1 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (35.0 mg, 68 μmol), (4-fluorophenyl)boronic acid (9.5 mg, 68 μmol) and tetrakis(triphenylphosphine)palladium(0) (3.9 mg, 3 μmol) were then added and the mixture was heated to 92° C. for 4 h. After cooling to RT, the reaction mixture was diluted with dichloromethane and the organic phase was washed with saturated aqueous ammonium chloride solution, dried and concentrated. The residue was taken up in dioxane (1.0 ml), and to this were added 1.0 M aqueous sodium carbonate solution (1.1 ml), (4-fluorophenyl)boronic acid (9.5 mg, 68 μmol) and tetrakis(triphenylphosphine)palladium(0) (3.9 mg, 3 μmol), and the mixture was once more heated to 92° C. for 7 h. After cooling to RT, the reaction mixture was concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (12.7 mg, 35% of theory).

[0661] ESI Mass [m/z]: 529.0 [M+H].sup.+

[0662] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.90-7.84 (m, 3H), 7.83 (s, 1H), 7.50-7.41 (m, 2H), 3.93 (s, 3H), 3.85-3.75 (m, 5H), 2.55-2.52 (m, 2H), 2.08 (s, 1H), 1.31 (t, 3H).

Example I-6

1-{4-[5-(Ethylsulfonyl)-1-methyl-4-(6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazol-2-yl)-1H-imidazol-2-yl]phenyl}cyclopropanecarbonitrile

[0663] ##STR00029##

[0664] A mixture of dioxane (1.0 ml) and 1.0 M aqueous sodium carbonate solution (1.1 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (35.0 mg, 68 μmol), 1-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]cyclopropanecarbonitrile (36.7 mg, 136 μmol) and tetrakis(triphenylphosphine)palladium(0) (7.8 mg, 7 μmol) were then added and the mixture was heated at 92° C. overnight. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the organic phase was washed with water, 1.0 M hydrochloric acid and saturated aqueous sodium chloride solution. The organic phase was then dried and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (48.7 mg, 85% purity, 53% of theory).

[0665] ESI Mass [m/z]: 576.3 [M+H].sup.+

[0666] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.88 (s, 1H), 7.86-7.81 (m, 3H), 7.54 (d, 2H), 3.94 (s, 3H), 3.84-3.77 (m, 5H), 1.89-1.82 (m, 2H), 1.67-1.60 (m, 2H), 1.31 (t, 3H).

Example I-7

2-[5-(Ethylsulfonyl)-1-methyl-2-{4-[1-(trifluoromethyl)cyclopropyl]phenyl}-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0667] ##STR00030##

[0668] A mixture of dioxane (2.6 ml) and 1.0 M aqueous sodium carbonate solution (3.1 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (82.1 mg, 160 μmol), 4,4,5,5-tetramethyl-2-{4-[1-(trifluoromethyl)cyclopropyl]phenyl}-1,3,2-dioxaborolane (50.0 mg, 160 μmol) and tetrakis(triphenylphosphine)palladium(0) (9.2 mg, 8 μmol) were then added and the mixture was heated at 92° C. overnight. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the organic phase was washed with water, 1.0 M hydrochloric acid and saturated aqueous sodium chloride solution. The organic phase was then dried and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (65.0 mg, 66% of theory).

[0669] ESI Mass [m/z]: 619.1 [M+H].sup.+

[0670] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.86-7.81 (m, 3H), 7.68 (d, 2H), 3.95 (s, 3H), 3.89-3.75 (m, 5H), 1.45-1.37 (m, 2H), 1.31 (t, 3H), 1.26-1.19 (m, 2H).

Example I-8

2-[2-Cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0671] ##STR00031##

[0672] A mixture of N-(7-amino-2,2,3,3-tetrafluoro-2,3-dihydro-1,4-benzodioxin-6-yl)-2-cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazole-4-carboxamide (163 mg, 341 μmol) and toluene-4-sulfonic acid monohydrate (195 mg, 1022 μmol) in toluene (3.4 ml) was heated to boiling for 6 h. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the organic phase was washed with water until a neutral reaction was achieved, and dried and concentrated in order to obtain the title compound (149 mg, 93% purity, 88% of theory).

[0673] ESI Mass [m/z]: 461.3 [M+H].sup.+

[0674] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=12.98 (s, 1H), 7.76 (s, 1H), 7.52 (s, 1H), 3.96 (s, 3H), 3.96-3.92 (m, 2H), 2.25-2.13 (m, 1H), 1.25 (t, 3H), 1.11-1.01 (m, 4H).

Example I-9

2-[2-Cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0675] ##STR00032##

[0676] To an initial charge of 2-[2-cyclopropyl-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (135 mg, 293 μmol) in acetone (2.0 ml) were added potassium carbonate (142 mg, 1026 μmol) and iodomethane (46 μl, 733 μmol). The mixture was heated to boiling for 3 h. After cooling to RT, the reaction mixture was concentrated and the residue partitioned between dichloromethane and 1.0 M hydrochloric acid. The organic phase was washed with water, dried and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (74.0 mg, 93% purity, 49% of theory).

[0677] ESI Mass [m/z]: 475.4 [M+H].sup.+

[0678] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.84 (s, 1H), 7.78 (s, 1H), 3.96 (s, 3H), 3.73 (s, 3H), 3.67 (q, 2H), 2.25-2.17 (m, 1H), 1.24 (t, 3H), 1.12-0.97 (m, 4H).

Example I-10

2-[2-(4-Bromophenyl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0679] ##STR00033##

[0680] To an initial charge of 2-[2-bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (40.0 mg, 0.078 mmol) and 4-bromophenylboronic acid (31.3 mg, 0.156 mmol) in dioxane (3.0 ml), in a microwave vessel, were added 2.0 M aqueous sodium carbonate solution (195 μl, 0.390 mmol) and dichlorobis(tricyclohexylphosphine)palladium(II) (5.8 mg, 8.0 μmol). The mixture was degassed in an argon stream for 5 min before the vessel was sealed and was heated in the microwave reactor to 120° C. for 12 min. After cooling, tetrakis(triphenylphosphine)palladium(0) (9.0 mg, 8.0 μmol) was added and the mixture was heated once more to 120° C. for 24 min. After cooling, tetrakis(triphenylphosphine)palladium(0) (9.0 mg, 8.0 μmol) was again added and the mixture was heated once again to 120° C. for 1 h. Water and dichloromethane were added to the cooled reaction mixture, the phases were separated, and the organic phase was washed twice with water and then dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (9.1 mg, 20% of theory).

[0681] ESI Mass [m/z]: 589.1/591.1 [M+H].sup.+

[0682] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.83 (s, 1H), 7.83-7.75 (m, 4H), 3.94 (s, 3H), 3.82 (s, 3H), 3.79 (q, 2H), 1.31 (t, 3H).

Example I-11

2-{5-(Ethylsulfonyl)-2-[4-(1-fluorocyclopropyl)phenyl]-1-methyl-1H-imidazol-4-yl}-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0683] ##STR00034##

[0684] 2-[2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (45.0 mg, 88.0 μmol), 2-[4-(1-fluorocyclopropyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (46.0 mg, 175 μmol) and tetrakis(triphenylphosphine)palladium(0) (20.3 mg, 18.0 μmol) were initially charged in a microwave vessel and taken up in a degassed mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (438 μl, 438 μmol). The reaction mixture was heated in a microwave reactor to 120° C. for 30 minutes. After cooling to RT, water was added to the mixture and the latter was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (30.0 mg, 60% of theory).

[0685] ESI Mass [m/z]: 569.0 [M+H].sup.+

[0686] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.85-7.81 (m, 3H), 7.47 (d, 2H), 3.96 (s, 3H), 3.83 (s, 3H), 3.80 (q, 2H), 1.62-1.49 (m, 2H), 1.36-1.24 (m, 5H).

Example I-12

2-[2-(3-Bromophenyl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0687] ##STR00035##

[0688] 2-[2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (45.0 mg, 88.0 μmol), 4-bromophenylboronic acid (35.2 mg, 156 μmol) and tetrakis(triphenylphosphine)palladium(0) (20.3 mg, 18.0 μmol) were initially charged in a microwave vessel and taken up in a degassed mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (438 μl, 438 μmol). The reaction mixture was heated in a microwave reactor to 120° C. for 30 minutes. After cooling to RT, water was added to the mixture and the latter was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (9.3 mg, 18% of theory).

[0689] ESI Mass [m/z]: 589.0/591.0 [M+H].sup.+

[0690] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.03-8.01 (m, 1H), 7.89 (s, 1H), 7.84-7.80 (m, 3H), 7.61-7.54 (m, 1H), 3.95 (s, 3H), 3.84-3.76 (m, 5H), 1.31 (t, 3H).

Example I-13

2-[2-(3-Chlorophenyl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0691] ##STR00036##

[0692] 2-[2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (45.0 mg, 88.0 μmol), 3-chlorophenylboronic acid (27.4 mg, 175 μmol) and tetrakis(triphenylphosphine)palladium(0) (20.3 mg, 18.0 μmol) were initially charged in a microwave vessel and taken up in a degassed mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (438 μl, 438 μmol). The reaction mixture was heated in a microwave reactor to 120° C. for 30 minutes. After cooling to RT, water was added to the mixture and the latter was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (26.2 mg, 99% purity, 54% of theory).

[0693] ESI Mass [m/z]: 545.0 [M+H].sup.+

[0694] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.90-7.88 (m, 2H), 7.83 (s, 1H), 7.80-7.77 (m, 1H), 7.70-7.60 (m, 2H), 3.95 (s, 3H), 3.83 (s, 3H), 3.79 (q, 2H), 1.31 (t, 3H).

Example I-14

2-[5-(Ethylsulfonyl)-2-(3-fluorophenyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0695] ##STR00037##

[0696] 2-[2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (45.0 mg, 88.0 μmol), 3-fluorophenylboronic acid (24.5 mg, 175 μmol) and tetrakis(triphenylphosphine)palladium(0) (20.3 mg, 18.0 μmol) were initially charged in a microwave vessel and taken up in a degassed mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (438 μl, 438 μmol). The reaction mixture was heated in a microwave reactor to 120° C. for 30 minutes. After cooling to RT, water was added to the mixture and the latter was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (22.5 mg, 49% of theory).

[0697] ESI Mass [m/z]: 529.2 [M+H].sup.+

[0698] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.83 (s, 1H), 7.71-7.62 (m, 3H), 7.49-7.43 (m, 1H), 3.96 (s, 3H), 3.83 (s, 3H), 3.80 (q, 2H), 1.31 (t, 3H).

Example I-15

2-{5-(Ethylsulfonyl)-1-methyl-2-[4-(trifluoromethyl)phenyl]-1H-imidazol-4-yl}-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0699] ##STR00038##

[0700] 2-[2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (45.0 mg, 88.0 μmol), [4-(trifluoromethyl)phenyl]boronic acid (33.3 mg, 175 μmol) and tetrakis(triphenylphosphine)palladium(0) (20.3 mg, 18.0 μmol) were initially charged in a microwave vessel and taken up in a degassed mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (438 μl, 438 μmol). The reaction mixture was heated in a microwave reactor to 120° C. for 30 minutes. After cooling to RT, water was added to the mixture and the latter was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (33.0 mg, 98% purity, 64% of theory).

[0701] ESI Mass [m/z]: 579.0 [M+H].sup.+

[0702] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.06 (d, 2H), 7.97 (d, 2H), 7.89 (s, 1H), 7.84 (s, 1H), 3.98 (s, 3H), 3.84 (s, 3H), 3.81 (q, 2H), 1.36-1.28 (m, 3H).

Example I-16

2-[5-(Ethylsulfonyl)-1-methyl-2-phenyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0703] ##STR00039##

[0704] 2-[2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (45.0 mg, 88.0 μmol), phenylboronic acid (21.4 mg, 175 μmol) and tetrakis(triphenylphosphine)palladium(0) (20.2 mg, 18.0 μmol) were initially charged in a microwave vessel and taken up in a degassed mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (438 μl, 438 μmol). The reaction mixture was heated in a microwave reactor to 120° C. for 30 minutes. After cooling to RT. water was added to the mixture and the latter was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (30.0 mg, 99% purity, 66% of theory).

[0705] ESI Mass [m/z]: 511.3 [M+H].sup.+

[0706] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.83 (s, 1H), 7.83-7.79 (m, 2H), 7.63-7.58 (m, 3H), 3.95 (s, 3H), 3.83 (s, 3H), 3.80 (q, 2H), 1.35-1.29 (m, 3H).

Example I-17

2-[5-(Ethylsulfonyl)-1-methyl-2-{3-[1-(trifluoromethyl)cyclopropyl]phenyl}-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0707] ##STR00040##

[0708] A mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (0.4 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (41.0 mg, 80 μmol), 4,4,5,5-tetramethyl-2-{3-[1-(trifluoromethyl)cyclopropyl]phenyl}-1,3,2-dioxaborolane (64.8 mg, 160 μmol) and tetrakis(triphenylphosphine)palladium(0) (18.5 mg, 16 μmol) were then added and the mixture was heated in a microwave reactor to 120° C. for 30 min. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (33.5 mg, 68% of theory).

[0709] ESI Mass [m/z]: 619.2 [M+H].sup.+

[0710] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.90-7.87 (m, 2H), 7.84 (s, 1H), 7.81 (d, 1H), 7.69 (d, 1H), 7.65-7.60 (m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.78 (q, 2H), 1.42-1.38 (m, 2H), 1.31 (t, 3H), 1.25-1.21 (m, 2H).

Example I-18

2-[2-(6-Cyclopropylpyridin-3-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0711] ##STR00041##

[0712] A mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (0.4 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (41.0 mg, 80 μmol), 2-cyclopropyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine (39.2 mg, 160 μmol) and tetrakis(triphenylphosphine)palladium(0) (18.5 mg, 16 μmol) were then added and the mixture was heated in a microwave reactor to 120° C. for 30 min. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (28.2 mg, 64% of theory).

[0713] ESI Mass [m/z]: 552.3 [M+H].sup.+

[0714] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.80 (d, 1H), 8.07 (dd, 1H), 7.89 (s, 1H), 7.83 (s, 1H), 7.52 (d, 1H), 3.95 (s, 3H), 3.83 (s, 3H), 3.80 (q, 2H), 2.26-2.20 (m, 1H), 1.31 (t, 3H), 1.08-1.00 (m, 4H).

Example I-19

2-[2-(5-Chloro-2-thienyl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0715] ##STR00042##

[0716] A mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (0.4 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (41.0 mg, 80 μmol), 2-(5-chloro-2-thienyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (39.1 mg, 160 μmol) and tetrakis(triphenylphosphine)palladium(0) (18.4 mg, 16 μmol) were then added and the mixture was heated in a microwave reactor to 120° C. for 30 min. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (16.9 mg, 38% of theory).

[0717] ESI Mass [m/z]: 551.1/553.0 [M+H].sup.+

[0718] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.83 (s, 1H), 7.65 (d, 1H), 7.34 (d, 1H), 4.08 (s, 3H), 3.79 (s, 3H), 3.73 (q, 2H), 1.28 (t, 3H).

Example I-20

2-{5-(Ethylsulfonyl)-2-[3-(1-fluorocyclopropyl)phenyl]-1-methyl-1H-imidazol-4-yl}-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0719] ##STR00043##

[0720] A mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (0.4 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (41.0 mg, 80 μmol), 2-[3-(1-fluorocyclopropyl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (50.4 mg, 192 μmol) and tetrakis(triphenylphosphine)palladium(0) (18.5 mg, 16 μmol) were then added and the mixture was heated in a microwave reactor to 120° C. for 30 min. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (29.3 mg, 97% purity, 60% of theory).

[0721] ESI Mass [m/z]: 569.0 [M+H].sup.+

[0722] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.89 (s, 1H), 7.83 (s, 1H), 7.77-7.69 (m, 1H), 7.67-7.59 (m, 2H), 7.50 (d, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.78 (q, 2H), 1.59-1.45 (m, 2H), 1.31 (t, 3H), 1.29-1.23 (m, 2H).

Example I-21

2-[2-(6-Chloropyridin-2-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0723] ##STR00044##

[0724] A mixture of 2-[2-bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (70.0 mg, 136 μmol), 2-chloro-6-(tributylstannyl)pyridine (71.3 mg, 177 μmol), lithium chloride (15.0 mg, 355 μmol), copper(I) iodide (2.6 mg, 14 μmol) and tetrakis(triphenylphosphine)palladium(0) (31.5 mg, 27 μmol) in degassed dioxane (3.0 ml) was heated in a microwave reactor to 150° C. for 1 h. After cooling to RT, the reaction mixture was filtered through a layer of silica gel and washed with a mixture of dichloromethane and triethylamine (95:5 vol %), and the filtrate was concentrated. Repeated chromatographic purification of the residue first by means of preparative HPLC and then on silica gel afforded the title compound (16.0 mg, 98% purity, 21% of theory).

[0725] ESI Mass [m/z]: 546.3/538.1 [M+H].sup.+

[0726] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.17 (m, 1H), 8.07-8.12 (m, 1H), 7.90 (s, 1H), 7.84 (s, 1H), 7.72 (m, 1H), 5.75 (s, 1H), 4.30 (s, 3H), 3.81 (s, 3H), 3.76 (m, 2H), 1.29 (m, 3H).

Example I-22

2-[2-(6′-Chloro[2,2′-b]pyridin]-6-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0727] ##STR00045##

[0728] A mixture of 2-[2-bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (70.0 mg, 136 μmol), 2-chloro-6-(tributylstannyl)pyridine (71.3 mg, 177 μmol), lithium chloride (15.0 mg, 355 μmol), copper(I) iodide (2.6 mg, 14 μmol) and tetrakis(triphenylphosphine)palladium(0) (31.5 mg, 27 μmol) in degassed dioxane (3.0 ml) was heated in a microwave reactor to 150° C. for 1 h. After cooling to RT, the reaction mixture was filtered through a layer of silica gel and washed with a mixture of dichloromethane and triethylamine (95:5 vol %), and the filtrate was concentrated. Repeated chromatographic purification of the residue first by means of preparative HPLC and then on silica gel afforded the title compound (4.3 mg, 98% purity, 5% of theory).

[0729] ESI Mass [m/z]: 623.3 [M+H].sup.+

[0730] .sup.1H-NMR (600 MHz, DMF-d.sub.7): δ [ppm]=8.59 (d, 1H), 8.52 (d, 1H), 8.37 (d, 1H), 8.28 (m, 1H), 8.14-8.19 (m, 1H), 7.92 (s, 1H), 7.82 (s, 1H), 7.70 (d, 1H), 4.62 (s, 3H), 4.01 (s, 3H), 3.93 (m, 2H), 1.43 (m, 3H).

Example I-23

2-[2-(3-Cyclopropyl-1H-1,2,4-triazol-1-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0731] ##STR00046##

[0732] A mixture of 2-[2-bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (40.0 mg, 78 μmol), 3-cyclopropyl-1H-1,2,4-triazole (8.5 mg, 78 μmol) and potassium carbonate (10.7 mg, 78 μmol) in DMF was heated at 96° C. overnight. Subsequently, 3-cyclopropyl-1H-1,2,4-triazole (8.5 mg, 78 μmol) and potassium carbonate (10.7 mg, 78 μmol) were again added, and the mixture was stirred at 96° C. for a further 5 h. After cooling to RT, the reaction mixture was diluted with dichloromethane and water. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (23.0 mg, 98% purity, 53% of theory).

[0733] ESI Mass [m/z]: 542.2 [M+H].sup.+

[0734] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=9.04 (s, 1H), 7.90 (s, 1H), 7.85 (s, 1H), 3.94 (s, 3H), 3.80-3.85 (m, 5H), 2.12-2.19 (m, 1H), 1.31 (m, 3H), 0.99-1.09 (m, 2H), 0.94 (m, 2H).

Example I-24

2-[2-(5-Bromopyridin-2-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0735] ##STR00047##

[0736] A mixture of 2-[2-bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (70.0 mg, 136 μmol), 5-bromo-2-(tributylstannyl)pyridine (79.3 mg, 177 μmol), lithium chloride (15.0 mg, 355 μmol), copper(I) iodide (2.6 mg, 14 μmol) and tetrakis(triphenylphosphine)palladium(0) (31.5 mg, 27 μmol) in degassed dioxane (3.0 ml) was heated in a microwave reactor to 150° C. for 1 h. After cooling to RT, the reaction mixture was filtered through a layer of silica gel and washed with a mixture of dichloromethane and triethylamine (95:5 vol %), and the filtrate was concentrated. Repeated chromatographic purification of the residue first by means of preparative HPLC and then on silica gel afforded the title compound (4.5 mg, 6% of theory).

[0737] ESI Mass [m/z]: 589.9/591.9 [M+H].sup.+

[0738] .sup.1H-NMR (400 MHz, Acetonitrile-d.sub.3): 6 [ppm]=8.81-8.83 (m, 1H), 8.08-8.12 (m, 2H), 7.59 (s, 1H), 7.47 (s, 1H), 4.34 (s, 3H), 3.81 (s, 3H), 3.66 (m, 2H), 1.34 (m, 3H).

Example I-25

2-[2-(5-Bromo[2,3′-b]pyridin]-6′-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0739] ##STR00048##

[0740] A mixture of 2-[2-bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (70.0 mg, 136 μmol), 5-bromo-2-(tributylstannyl)pyridine (79.3 mg, 177 μmol), lithium chloride (15.0 mg, 355 μmol), copper(I) iodide (2.6 mg, 14 μmol) and tetrakis(triphenylphosphine)palladium(0) (31.5 mg, 27 μmol) in degassed dioxane (3.0 ml) was heated in a microwave reactor to 150° C. for 1 h. After cooling to RT, the reaction mixture was filtered through a layer of silica gel and washed with a mixture of dichloromethane and triethylamine (95:5 vol %), and the filtrate was concentrated. Repeated chromatographic purification of the residue first by means of preparative HPLC and then on silica gel afforded the title compound (2.7 mg, 3% of theory).

[0741] ESI Mass [m/z]: 666.9/668.9 [M+H]+

[0742] .sup.1H-NMR (400 MHz, Acetonitrile-d.sub.3): 6 [ppm]=9.33-9.36 (m, 1H), 8.81-8.83 (m, 1H), 8.53 (m, 1H), 8.28 (m, 1H), 8.09 (m, 1H), 7.93 (d, 1H), 7.60 (s, 1H), 7.48 (s, 1H), 4.43 (s, 3H), 3.84 (s, 3H), 3.68 (m, 2H), 1.36 (m, 3H).

Example I-26

2-[5-(Ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0743] ##STR00049##

[0744] To a solution of 6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (345 mg, 1.32 mmol) in dry dioxane (15.0 ml) was added 2,2,6,6-tetramethylpiperidinylzinc chloride lithium chloride complex (1.3 M solution in THF, 1.20 ml, 1.58 mmol) within 5 min, and the mixture was stirred at RT for 20 min. Subsequently, a solution of tetrakis(triphenylphosphine)palladium(0) (152 mg, 132 μmol) in dioxane (5.0 ml) and a solution of 5-(ethylsulfanyl)-4-iodo-1-methyl-1H-imidazole (353 mg, 1.32 mmol) in dioxane (5.0 ml) were added and the mixture was stirred at 115° C. (oil bath temperature) for 2 h. After cooling to RT, the reaction mixture was introduced into semisaturated aqueous ammonium chloride solution (40 ml) and diluted with ethyl acetate (40 ml). In the course of this, a portion of the target compound precipitated out. Filtering off and drying the solids afforded a first fraction of the title compound (158 mg, 30% of theory).

[0745] A second fraction of the title compound was obtained from the filtrate. To this end, the phases were separated and the aqueous phase was extracted with ethyl acetate (2×40 ml). The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded a second fraction of the title compound (166 mg, 31% of theory).

[0746] ESI Mass [m/z]: 403.5 [M+H].sup.+

[0747] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.10 (s, 1H), 7.81 (s, 1H), 7.77 (s, 1H), 3.99 (s, 3H), 3.75 (s, 3H), 2.96 (m, 2H), 1.07 (m, 3H).

Example I-27

1-{6-[5-(Ethylsulfanyl)-1-methyl-4-(6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazol-2-yl)-1H-imidazol-2-yl]pyridin-2-yl}cyclopropanecarbonitrile

[0748] ##STR00050##

[0749] To a solution of 2-[5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (82.5 mg, 205 μmol) in dry dioxane (15.0 ml) was added 2,2,6,6-tetramethylpiperidinylzinc chloride lithium chloride complex (1.3 M solution in THF, 186 μl, 246 μmol) within 5 min, and the mixture was stirred at RT for 20 min. Subsequently, a solution of tetrakis(triphenylphosphine)palladium(0) (23.7 mg, 21 μmol) in dioxane (5.0 ml) and a solution of 1-(6-bromopyridin-2-yl)cyclopropanecarbonitrile (45.7 mg, 205 μmol) in dioxane (5.0 ml) were added and the mixture was stirred at 115° C. (oil bath temperature) for 2 h. After cooling to RT, the reaction mixture was introduced into semisaturated aqueous ammonium chloride solution (40 ml) and diluted with ethyl acetate (40 ml). The phases were separated and the aqueous phase was extracted with ethyl acetate (2×40 ml). The combined organic phases were dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (19 mg, 40% purity, 7% of theory).

[0750] ESI Mass [m/z]: 545.2 [M+H].sup.+

[0751] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.14 (d, 1H), 7.99-8.04 (m, 1H), 7.86 (s, 1H), 7.81 (s, 1H), 7.59 (br m, 1H), 4.18 (s, 3H), 4.05 (s, 3H), 2.96-3.03 (m, 2H), 1.82-1.94 (m, 4H), 1.11 (m, 3H).

Example I-28

1-{6-[5-(Ethylsulfonyl)-1-methyl-4-(6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazol-2-yl)-1H-imidazol-2-yl]pyridin-2-yl}cyclopropanecarbonitrile

[0752] ##STR00051##

[0753] To an initial charge of 1-{6-[5-(ethylsulfanyl)-1-methyl-4-(6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazol-2-yl)-1H-imidazol-2-yl]pyridin-2-yl}cyclopropanecarbonitrile (17.0 mg, 31.0 μmol) in dichloromethane (20.0 ml) were added formic acid (12 μl, 312 μmol) and hydrogen peroxide (35% aqueous solution, 27 μl, 312 μmol). The mixture was stirred at RT overnight. Subsequently, water (50.0 ml) and saturated aqueous sodium bisulfite solution (15.0 ml) were added to the reaction mixture and the latter was stirred for 1 h. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were washed with water, dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (7.5 mg, 42% of theory).

[0754] ESI Mass [m/z]: 577.0 [M+H].sup.+

[0755] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.03-8.11 (m, 2H), 7.90 (s, 1H), 7.84 (s, 1H), 7.67 (m, 1H), 4.30 (s, 3H), 3.80 (s, 3H), 3.76 (m, 2H), 1.91-1.95 (m, 2H), 1.82-1.86 (m, 2H), 1.29 (m, 3H).

Example I-29

2-[2-(6-Bromopyridin-2-yl)-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0756] ##STR00052##

[0757] To a solution of 2-[5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (82.5 mg, 205 μmol) in dry dioxane (15.0 ml) was added 2,2,6,6-tetramethylpiperidinylzinc chloride lithium chloride complex (1.3 M solution in THF, 186 μl, 246 μmol) within 5 min, and the mixture was stirred at RT for 20 min. Subsequently, a solution of tetrakis(triphenylphosphine)palladium(0) (23.7 mg, 21 μmol) in dioxane (5.0 ml) and a solution of 2,6-dibromopyridine (48.6 mg, 205 μmol) in dioxane (5.0 ml) were added and the mixture was stirred at 115° C. (oil bath temperature) for 2 h. After cooling to RT, the reaction mixture was introduced into semisaturated aqueous ammonium chloride solution (40 ml) and diluted with ethyl acetate (40 ml). The insoluble constituents were filtered off. The phases were separated and the aqueous phase was extracted with ethyl acetate (2×40 ml). The combined organic phases were dried over sodium sulfate and concentrated. The residue and the solids previously filtered off were combined. Purification of the thus-obtained crude product by means of preparative HPLC afforded the title compound (28.2 mg, 90% purity, 22% of theory).

[0758] ESI Mass [m/z]: 558.0/560.0 [M+H].sup.+

[0759] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.23 (m, 1H), 7.91-7.97 (m, 1H), 7.86 (s, 1H), 7.82 (s, 1H), 7.75 (m, 1H), 4.17 (s, 3H), 4.05 (s, 3H), 3.01 (m, 2H), 1.11 (m, 3H).

Example I-30

2-[2-(6-Bromopyridin-2-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0760] ##STR00053##

[0761] To an initial charge of 2-[2-(6-bromopyridin-2-yl)-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (25.0 mg, 45.0 μmol) in dichloromethane (20.0 ml) were added formic acid (17 μl, 448 μmol) and hydrogen peroxide (35% aqueous solution, 39 μl, 448 μmol). The mixture was stirred at RT overnight. Subsequently, water (50.0 ml) and saturated aqueous sodium bisulfite solution (15.0 ml) were added to the reaction mixture and the latter was stirred for 1 h. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were washed with water, dried over sodium sulfate and concentrated. Purification of the residue by means of preparative HPLC afforded the title compound (13.7 mg, 52% of theory).

[0762] ESI Mass [m/z]: 590.0/592.0 [M+H].sup.+

[0763] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.85 (d, 1H), 8.15-8.21 (m, 2H), 7.90 (s, 1H), 7.84 (s, 1H), 4.31 (s, 3H), 3.82 (s, 3H), 3.77 (m, 2H), 1.29 (m, 3H).

Example I-31

2-[2-(5-Chloropyridin-2-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0764] ##STR00054##

[0765] A mixture of 2-[2-bromo-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (90.0 mg, 175 μmol), 5-chloro-2-(tributylstannyl)pyridine (91.7 mg, 228 μmol), lithium chloride (19.3 mg, 456 μmol), copper(I) iodide (3.3 mg, 18 μmol) and tetrakis(triphenylphosphine)palladium(0) (40.5 mg, 35 μmol) in degassed dioxane (3.0 ml) was heated in a microwave reactor to 150° C. for 1 h. After cooling to RT, the reaction mixture was filtered through a layer of silica gel and washed with a mixture of dichloromethane and triethylamine (95:5 vol %), and the filtrate was concentrated. Chromatographic purification of the residue by means of preparative HPLC afforded the title compound (57.8 mg, 98% purity, 59% of theory).

[0766] ESI Mass [m/z]: 546.0/548.0 [M+H]+

[0767] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=8.85 (d, 1H), 8.15-8.21 (m, 2H), 7.90 (s, 1H), 7.84 (s, 1H), 4.31 (s, 3H), 3.82 (s, 3H), 3.77 (q, 2H), 1.29 (m, 3H).

Example I-32

6-[5-(Ethylsulfonyl)-1-methyl-4-(6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazol-2-yl)-1H-imidazol-2-yl]nicotinonitrile

[0768] ##STR00055##

[0769] To a degassed mixture of water (170 μl) and cyclopentyl methyl ether (430 μl) were added 2-[2-(5-chloropyridin-2-yl)-5-(ethylsulfonyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (37.0 mg, 68 μmol), allylpalladium chloride dimer (7.9 mg, 22 μmol), potassium hexacyanoferrate trihydrate (57.3 mg, 136 μmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (Xphos, 13.9 mg, 28 μmol) and the reaction mixture was heated at 100° C. overnight. After cooling to RT, the mixture was diluted with water and extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate and concentrated. Purification of the thus-obtained crude product by means of preparative HPLC afforded the title compound (18.7 mg, 51% of theory).

[0770] ESI Mass [m/z]: 537.4 [M+H].sup.+

[0771] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=9.23 (d, 1H), 8.52 (m, 1H), 8.35 (d, 1H), 7.91 (s, 1H), 7.85 (s, 1H), 4.35 (s, 3H), 3.82 (s, 3H), 3.75-3.81 (m, 2H), 1.29 (m, 3H).

Example I-33

2-[2-(4-Chlorophenyl)-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0772] ##STR00056##

[0773] A mixture of dioxane (3.0 ml) and 1.0 M aqueous sodium carbonate solution (0.5 ml) was degassed in an argon stream for 30 min. 2-[2-Bromo-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (50.0 mg, 104 μmol), 4-chlorophenylboronic acid (32.5 mg, 208 μmol) and tetrakis(triphenylphosphine)palladium(0) (24.0 mg, 21 μmol) were then added and the mixture was heated in a microwave reactor to 120° C. for 30 min. After cooling to RT, the reaction mixture was concentrated to dryness and then taken up in dichloromethane and water. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried over sodium sulfate and concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (30.3 mg, 89% purity, 51% of theory).

[0774] ESI Mass [m/z]: 513.0/515.0 [M+H].sup.+

[0775] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.85-7.88 (m, 2H), 7.83 (s, 1H), 7.80 (s, 1H), 7.60-7.66 (m, 2H), 4.03 (s, 3H), 3.86 (s, 3H), 3.00 (m, 2H), 1.13 (m, 3H).

Example I-34

rac-2-[2-(4-Chlorophenyl)-5-(ethylsulfonimidoyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole

[0776] ##STR00057##

[0777] To a solution of 2-[2-(4-chlorophenyl)-5-(ethylsulfanyl)-1-methyl-1H-imidazol-4-yl]-6,6,7,7-tetrafluoro-1-methyl-6,7-dihydro-1H-[1,4]dioxino[2,3-f]benzimidazole (30.0 mg, 94% purity, 55 μmol) in dichloromethane and methanol were added ammonium carbamate (8.6 mg, 110 μmol) and (diacetoxyiodo)benzene (45.2 mg, 137 μmol) and the suspension was stirred in a closed reaction vessel at RT for 1 h. Subsequently, the reaction mixture was concentrated. Column chromatography purification of the residue on silica gel afforded the title compound (16.4 mg, 95% purity, 52% of theory).

[0778] ESI Mass [m/z]: 544.4/546.2 [M+H].sup.+

[0779] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm]=7.87 (s, 1H), 7.79-7.83 (m, 3H), 7.63-7.68 (m, 2H), 4.76 (s, 1H), 3.98 (s, 3H), 3.76 (s, 3H), 3.42-3.58 (m, 2H), 1.23 (m, 3H).

[0780] In analogy to the examples and according to the above-described preparation processes, the following compounds of the formula (I) can be obtained:

TABLE-US-00001 Example Structure NMR data I-1 [00058] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.70-7.48 (m, 2H), 3.72 (s, 3H), 3.03 (q, 2H), 1.11 (t, 3H). I-2 [00059] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 13.37 (s, 1H), 7.81 (br s, 1H), 7.53 (br s, 1H), 4.03 (q, 2H), 3.91 (s, 3H), 1.28 (t, 3H). I-3 [00060] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.83 (s, 1H), 3.91 (s, 3H), 3.77 (s, 3H), 3.73 (q, 2H), 1.26 (t, 3H). I-4 [00061] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.87-7.79 (m, 3H), 7.67 (d, 2H), 3.95 (s, 3H), 3.84-3.76 (m, 5H), 1.31 (t, 3H). I-5 [00062] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.90-7.84 (m, 3H), 7.83 (s, 1H), 7.50-7.41 (m, 2H), 3.93 (s, 3H), 3.85-3.75 (m, 5H), 2.55-2.52 (m, 2H), 2.08 (s, 1H), 1.31 (t, 3H). I-6 [00063] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.88 (s, 1H), 7.86-7.81 (m, 3H), 7.54 (d, 2H), 3.94 (s, 3H), 3.84-3.77 (m, 5H), 1.89- 1.82 (m, 2H), 1.67-1.60 (m, 2H), 1.31 (t, 3H). I-7 [00064] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.86-7.81 (m, 3H), 7.68 (d, 2H), 3.95 (s, 3H), 3.89-3.75 (m, 5H), 1.45- 1.37 (m, 2H), 1.31 (t, 3H), 1.26-1.19 (m, 2H). I-8 [00065] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 12.98 (s, 1H), 7.76 (s, 1H), 7.52 (s, 1H), 3.96 (s, 3H), 3.96-3.92 (m, 2H), 2.25-2.13 (m, 1H), 1.25 (t, 3H), 1.11-1.01 (m, 4H). I-9 [00066] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.84 (s, 1H), 7.78 (s, 1H), 3.96 (s, 3H), 3.73 (s, 3H), 3.67 (q, 2H), 2.25-2.17 (m, 1H), 1.24 (t, 3H), 1.12-0.97 (m, 4H). I-10 [00067] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.83 (s, 1H), 7.83-7.75 (m, 4H), 3.94 (s, 3H), 3.82 (s, 3H), 3.79 (q, 2H), 1.31 (t, 3H). I-11 [00068] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.85-7.81 (m, 3H), 7.47 (d, 2H), 3.96 (s, 3H), 3.83 (s, 3H), 3.80 (q, 2H), 1.62-1.49 (m, 2H), 1.36-1.24 (m, 5H). I-12 [00069] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.03-8.01 (m, 1H), 7.89 (s, 1H), 7.84-7.80 (m, 3H), 7.61-7.54 (m, 1H), 3.95 (s, 3H), 3.84-3.76 (m, 5H), 1.31 (t, 3H). I-13 [00070] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.90-7.88 (m, 2H), 7.83 (s, 1H), 7.80-7.77 (m, 1H), 7.70-7.60 (m, 2H), 3.95 (s, 3H), 3.83 (s, 3H), 3.79 (q, 2H), 1.31 (t, 3H). I-14 [00071] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.83 (s, 1H), 7.71-7.62 (m, 3H), 7.49-7.43 (m, 1H), 3.96 (s, 3H), 3.83 (s, 3H), 3.80 (q, 2H), 1.31 (t, 3H). I-15 [00072] .sup.1H-NMR (400 MHz. DMSO-d.sub.6): δ [ppm] = 8.06 (d, 2H), 7.97 (d, 2H), 7.89 (s, 1H), 7.84 (s, 1H), 3.98 (s, 3H), 3.84 (s, 3H), 3.81 (q, 2H), 1.36-1.28 (m, 3H). I-16 [00073] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.83 (s, 1H), 7.83-7.79 (m, 2H), 7.63-7.58 (m, 3H), 3.95 (s, 3H), 3.83 (s, 3H), 3.80 (q, 2H), 1.35-1.29 (m, 3H). I-17 [00074] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.90-7.87 (m, 2H), 7.84 (s, 1H), 7.81 (d, 1H), 7.69 (d, 1H), 7.65-7.60 (m, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.78 (q, 2H), 1.42-1.38 (m, 2H), 1.31 (t, 3H), 1.25-1.21 (m, 2H). I-18 [00075] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.80 (d, 1H), 8.07 (dd, 1H), 7.89 (s, 1H), 7.83 (s, 1H), 7.52 (d, 1H), 3.95 (s, 3H), 3.83 (s, 3H), 3.80 (q, 2H), 2.26-2.20 (m, 1H), 1.31 (t, 3H), 1.08-1.00 (m, 4H). I-19 [00076] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.83 (s, 1H), 7.65 (d, 1H), 7.34 (d, 1H), 4.08 (s, 3H), 3.79 (s, 3H), 3.73 (q, 2H), 1.28 (t, 3H). I-20 [00077] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.83 (s, 1H), 7.77-7.69 (m, 1H), 7.67-7.59 (m, 2H), 7.50 (d, 1H), 3.94 (s, 3H), 3.82 (s, 3H), 3.78 (q, 2H), 1.59-1.45 (m, 2H), 1.31 (t, 3H), 1.29-1.23 (m, 2H). I-21 [00078] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.17 (m, 1H), 8.07-8.12 (m, 1H), 7.90 (s, 1H), 7.84 (s, 1H), 7.72 (m, 1H), 5.75 (s, 1H), 4.30 (s, 3H), 3.81 (s, 3H), 3.76 (m, 2H), 1.29 (m, 3H). I-22 [00079] .sup.1H-NMR (600 MHz, DMSO-d.sub.6): δ [ppm] = 8.59 (d, 1H), 8.52 (d, 1H), 8.37 (d, 1H), 8.28 (m, 1H), 8.14-8.19 (m, 1H), 7.92 (s, 1H), 7.82 (s, 1H), 7.70 (d, 1H), 4.62 (s, 3H), 4.01 (s, 3H), 3.93 (m, 2H), 1.43 (m, 3H). I-23 [00080] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 9.04 (s, 1H), 7.90 (s, 1H), 7.85 (s, 1H), 3.94 (s, 3H), 3.80-3.85 (m, 5H), 2.12-2.19 (m, 1H), 1.31 (m, 3H), 0.99-1.09 (m, 2H), 0.94 (m, 2H). I-24 [00081] .sup.1H-NMR (400 MHz, Acetonitrile-d.sub.3): δ [ppm] = 8.81-8.83 (m, 1H), 8.08-8.12 (m, 2H), 7.59 (s, 1H), 7.47 (s, 1H), 4.34 (s, 3H), 3.81 (s, 3H), 3.66 (m, 2H), 1.34 (m, 3H). I-25 [00082] .sup.1H-NMR (400 MHz, Acetonitrilc-d.sub.3): δ [ppm] = 9.33-9.36 (m, 1H), 8.81-8.83 (m, 1H), 8.53 (m, 1H), 8.28 (m, 1H), 8.09 (m, 1H), 7.93 (d, 1H), 7.60 (s, 1H), 7.48 (s, 1H), 4.43 (s, 3H), 3.84 (s, 3H), 3.68 (m, 2H), 1.36 (m, 3H). I-26 [00083] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.10 (s, 1H), 7.81 (s, 1H), 7.77 (s, 1H), 3.99 (s, 3H), 3.75 (s, 3H), 2.96 (m, 2H), 1.07 (m, 3H). I-27 [00084] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.14 (d, 1H), 7.99-8.04 (m, 1H), 7.86 (s, 1H), 7.81 (s, 1H), 7.59 (br m, 1H), 4.18 (s, 3H), 4.05 (s, 3H), 2.96-3.03 (m, 2H), 1.82-1.94 (m, 4H), 1.11 (m, 3H). I-28 [00085] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.03-8.11 (m, 2H), 7.90 (s, 1H), 7.84 (s, 1H), 7.67 (m, 1H), 4.30 (s, 3H), 3.80 (s, 3H), 3.76 (m, 2H), 1.91-1.95 (m, 2H), 1.82-1.86 (m, 2H), 1.29 (m, 3H). I-29 [00086] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.23 (m, 1H), 7.91-7.97(m, 1H), 7.86 (s, 1H), 7.82 (s, 1H), 7.75 (m, 1H), 4.17 (s, 3H), 4.05 (s, 3H), 3.01 (m, 2H), 1.11 (m, 3H). I-30 [00087] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.85 (d, 1H), 8.15-8.21 (m, 2H), 7.90 (s, 1H), 7.84 (s, 1H), 4.31 (s, 3H), 3.82 (s, 3H), 3.77 (m, 2H), 1.29 (m, 3H). I-31 [00088] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.85 (d, 1H), 8.15-8.21 (m, 2H), 7.90 (s, 1H), 7.84 (s, 1H), 4.31 (s, 3H), 3.82 (s, 3H), 3.77 (q, 2H), 1.29 (m, 3H). I-32 [00089] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 9.23 (d, 1H), 8.52 (m, 1H), 8.35 (d, 1H), 7.91 (s, 1H), 7.85 (s, 1H), 4.35 (s, 3H), 3.82 (s, 3H), 3.75-3.81 (m, 2H), 1.29 (m, 3H). I-33 [00090] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.85-7.88 (m, 2H), 7.83 (s, 1H), 7.80 (s, 1H), 7.60-7.66 (m, 2H), 4.03 (s, 3H), 3.86 (s, 3H), 3.00 (m, 2H), 1.13 (m, 3H). I-34 [00091] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.87 (s, 1H), 7.79-7.83 (m, 3H), 7.63-7.68 (m, 2H), 4.76 (s, 1H), 3.98 (s, 3H), 3.76 (s, 3H), 3.42-3.58 (m, 2H), 1.23 (m, 3H). I-35 [00092] .sup.1H-NMR (400 MHz, Acetonitril-d.sub.3): δ [ppm] = 7.88 (s, 1H), 7.59 (s, 1H), 7.48 (s, 1H), 4.38 (s, 3H), 3.80 (s, 3H), 3.66 (m, 2H), 1.34 (m, 3H). I-36 [00093] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.89 (s, 1H), 7.83 (s, 1H), 7.73-7.76 (m, 1H), 7.70-7.71 (m, 1H), 7.54-7.66 (m, 2H), 3.93 (s, 3H), 3.82 (s, 3H), 3.79 (m, 2H), 1.79-1.85 (m, 2H), 1.59-1.66 (m, 2H), 1.31 (m, 3H). I-37 [00094] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.03 (d, 2H), 7.96 (d, 2H), 7.87 (s, 1H), 7.82 (s, 1H), 4.80 (s, 1H), 4.02 (s, 3H), 3.77 (s, 3H), 3.43-3.59 (m, 2H), 1.24 (m, 3H). I-38 [00095] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.81-7.87 (m, 4H), 7.40-7.46 (m, 2H), 4.75 (s, 1H), 3.97 (s, 3H), 3.76 (s, 3H), 3.39-3.58 (m, 2H), 1.23 (m, 3H). I-39 [00096] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.86 (s, 1H), 7.78-7.82 (m, 3H), 7.50-7.55 (m, 2H), 4.75 (s, 1H), 3.98 (s, 3H), 3.76 (s, 3H), 3.46-3.59 (m, 2H), 1.83-1.88 (m, 2H), 1.60-1.66 (m, 2H), 1.23 (m, 3H). I-40 [00097] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.88-7.91 (m, 4H), 7.84 (s, 1H), 3.95 (s, 3H), 3.83 (s, 3H), 3.77-3.81 (q, 2H), 1.31 (t, 3H). I-41 [00098] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.11 (d, 1H), 7.86-7.90 (m, 2H), 7.84 (s, 1 H), 7.79-7.83 (m, 1H), 3.96 (s, 3 H), 3.83 (s, 3 H), 3.76-3.81 (m, 2H), 1.31 (t, 3H). I-42 [00099] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.90 (s, 1H), 7.84 (s, 1H), 7.50-7.63 (m, 3H), 3.97 (s, 3H), 3.83 (s, 3H), 3.76-3.82 (m, 2H), 1.31 (t, 3H). I-43 [00100] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 8.17-8.21 (m, 1H), 8.06-8.16 (m, 2H), 7.90 (s, 1H), 7.84 (s, 1H), 3.98 (s, 3H), 3.84 (s, 3H), 3.78-3.83 (m, 2H), 1.32 (t, 3H). I-44 [00101] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ [ppm] = 7.92-7.97 (m, 1H), 7.89 (s, 1H), 7.87 (dd, 1H), 7.84 (s, 1H), 7.62 (dd, 1H), 3.96 (s, 3H), 3.82 (s, 3H), 3.79-3.81 (m, 2H), 1.31 (t, 3H).

USE EXAMPLES

[0781] Diabrotica Balteata—Spray Test

[0782] Solvent: 78 parts by weight of acetone [0783] 1.5 parts by weight of dimethylformamide

[0784] Emulsifier: alkylaryl polyglycol ether

[0785] An appropriate active ingredient formulation is produced by dissolving 1 part by weight of active ingredient with the stated parts by weight of solvent and making the solution up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. Further test concentrations are produced by diluting the formulation with emulsifier-containing water.

[0786] Pre-swollen wheat grains (Triticum aestivum) are incubated in a multiwell plate filled with agar and a little water for one day (5 seed grains per cavity). The germinated wheat grains are sprayed with an active ingredient formulation of the desired concentration. Subsequently, each cavity is infected with 10-20 beetle larvae of Diabrotica balteata.

[0787] After 7 days, efficacy in % is determined. 100% means that all wheat plants have grown as in the untreated, uninfected control; 0% means that no wheat plant has grown.

[0788] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 g/ha (=32 μg/cavity): I-2, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-18, I-20, I-21, I-24, I-30, I-32, I-34, I-36, I-38.

[0789] In this test, for example, the following compounds from the preparation examples show an efficacy of 80% at an application rate of 100 g/ha (=32 μg/cavity): I-4, I-23, I-37.

[0790] Meloidogyne Incognita Test

[0791] Solvent: 125.0 parts by weight of acetone

[0792] An appropriate active ingredient formulation is produced by mixing 1 part by weight of active ingredient with the stated amount of solvent and diluting the concentrate to the desired concentration with water.

[0793] Vessels are filled with sand, active ingredient solution, an egg/larvae suspension of the southern root-knot nematode (Meloidogyne incognita) and lettuce seeds. The lettuce seeds germinate and the plants develop. The galls develop on the roots.

[0794] After 14 days, the nematicidal efficacy in % is determined by the formation of galls. 100% means that no galls were found; 0% means that the number of galls on the treated plants corresponds to the untreated control.

[0795] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 20 ppm: I-6, I-38.

[0796] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 20 ppm: I-4, I-8, I-34, I-37.

[0797] Myzus persicae—Oral Test

[0798] Solvent: 100 parts by weight of acetone

[0799] An appropriate active ingredient formulation is produced by dissolving 1 part by weight of active ingredient with the specified parts by weight of solvent and making the solution up to the desired concentration with water.

[0800] 50 μl of the active ingredient formulation is transferred into microtiter plates and made up to a final volume of 200 μl with 150 μl of IPL41 insect medium (33%+15% sugar). Subsequently, the plates are sealed with parafilm, which a mixed population of green peach aphids (Myzus persicae) within a second microtiter plate is able to puncture and imbibe the solution.

[0801] After 5 days, efficacy in % is determined. 100% means that all of the aphids have been killed; 0% means that none of the aphids have been killed.

[0802] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 20 ppm: I-8.

[0803] Myzus persicae—Spray Test

[0804] Solvent: 78 parts by weight of acetone [0805] 1.5 parts by weight of dimethylformamide

[0806] Emulsifier: alkylaryl polyglycol ether

[0807] An appropriate active ingredient formulation is produced by dissolving 1 part by weight of active ingredient with the stated parts by weight of solvent and making the solution up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. Further test concentrations are produced by diluting the formulation with emulsifier-containing water.

[0808] Leaf disks of Chinese cabbage (Brassica pekinensis) infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active ingredient formulation of the desired concentration.

[0809] After 5 days, efficacy in % is determined. 100% means that all of the aphids have been killed; 0% means that none of the aphids have been killed.

[0810] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 100 g/ha: 1-16, 1-34, 1-38.

[0811] Nezara viridula—Spray Test

[0812] Solvent: 78.0 parts by weight of acetone [0813] 1.5 parts by weight of dimethylformamide

[0814] Emulsifier: alkylaryl polyglycol ether

[0815] An appropriate active ingredient formulation is produced by dissolving 1 part by weight of active ingredient with the stated parts by weight of solvent and making the solution up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. Further test concentrations are produced by diluting the formulation with emulsifier-containing water.

[0816] Barley plants (Hordeum vulgare) are sprayed with an active ingredient formulation of the desired concentration and are infected with larvae of the Southern green shield bug (Nezara viridula).

[0817] After 4 days, efficacy in % is determined. 100% means that all of the shield bugs have been killed; 0% means that none of the shield bugs have been killed.

[0818] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 500 g/ha: I-6, I-10, I-11, I-15, I-16, I-18, I-19, I-21, I-23, I-24, I-28, I-30.

[0819] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 500 g/ha: I-14, I-20, I-36, I-38.

[0820] Nilaparvata lugens Test

[0821] Solvent: 78.0 parts by weight of acetone [0822] 1.5 parts by weight of dimethylformamide

[0823] Emulsifier: alkylaryl polyglycol ether

[0824] An appropriate active ingredient formulation is produced by dissolving 1 part by weight of active ingredient with the stated parts by weight of solvent and making the solution up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. Further test concentrations are produced by diluting the formulation with emulsifier-containing water.

[0825] Rice plants (Oryza sativa) are sprayed with the active ingredient formulation of the desired concentration and then infected with the brown planthopper (Nilaparvata lugens).

[0826] After 4 days, efficacy in % is determined. 100% means that all of the planthoppers have been killed; 0% means that none of the planthoppers have been killed.

[0827] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 500 g/ha: I-28, I-30.

[0828] In this test, for example, the following compounds from the preparation examples show an efficacy of 90% at an application rate of 500 g/ha: I-21.

[0829] Spodoptera frugiuerda—Spray Test

[0830] Solvent: 78.0 parts by weight of acetone [0831] 1.5 parts by weight of dimethylformamide

[0832] Emulsifier: alkylaryl polyglycol ether

[0833] An appropriate active ingredient formulation is produced by dissolving 1 part by weight of active ingredient with the stated parts by weight of solvent and making the solution up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. Further test concentrations are produced by diluting the formulation with emulsifier-containing water.

[0834] Leaf disks of maize (Zea mays) are sprayed with an active ingredient formulation of the desired concentration and, after drying, populated with caterpillars of the fall armyworm (Spodopterafrugiperda).

[0835] After 7 days, efficacy in % is determined. 100% means that all of the caterpillars have been killed; 0% means that none of the caterpillars have been killed.

[0836] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 500 g/ha: I-8.

[0837] In this test, for example, the following compounds from the preparation examples show an efficacy of 100% at an application rate of 100 g/ha: I-2, I-4, I-5, I-6, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-18, I-19, 1-20, I-21, I-23, I-24, I-25, I-28, I-30, I-31, I-32, I-34, I-36, I-37, I-38, I-39.

[0838] In this test, for example, the following compounds from the preparation examples show an efficacy of 83% at an application rate of 100 g/ha: I-9.

[0839] Myzus persicae—spray test

[0840] Solvent: 14 parts by weight of dimethylformamide

[0841] Emulsifier: alkylaryl polyglycol ether

[0842] An appropriate active ingredient formulation is produced by dissolving 1 part by weight of active ingredient with the stated parts by weight of solvent and making the solution up to the desired concentration with water containing an emulsifier concentration of 1000 ppm. Further test concentrations are produced by diluting the formulation with emulsifier-containing water. If the addition of ammonium salts or/and penetration enhancers is required, these are each added in a concentration of 1000 ppm to the formulation solution.

[0843] Bell pepper plants (Capsicum annuum) severely infested with the green peach aphid (Myzus persicae) are treated by spraying with the active ingredient formulation in the desired concentration.

[0844] After 6 days, the kill in % is determined. 100% means that all of the aphids have been killed; 0% means that none of the aphids have been killed.

[0845] In this test, for example, the following compounds from the preparation examples show an efficacy of 99% at an application rate of 20 ppm: I-9.